The present thesis deals with synthesis of free alloy nanoparticles in immiscible alloy systems by the process of laser ablation under a liquid. In this process the alloy target is submerged in a liquid and the plume formed by the laser beam interaction with the target is confined in the liquid. The nanoparticles formed inside this plume and get quenched by the surrounding liquid yielding suspension of nanoparticles in the liquid. By the addition of suitable surfactants, these nanoparticles can be protected from other reactions and their size can be controlled by preventing further growth. We have selected immiscible alloys for the present study. These alloys tend to phase separate in melt as well as in solid depending on the value of the positive heat of mixing. We have used two binary alloys for the present study. These are alloys in Ag-Cu system and Fe-Cu system. In both these systems, there are reports of formation of extended solid solution due to kinetic factors during nonequilibrium processing like rapid solidification and mechanical alloying. In the present thesis we report synthesis of alloy nanoparticles of different compositions and sizes in these two systems and explore the nature of the phases that form in the small (nano) particles and their evolutionary pathways leading to the final microstructure. Microscopic techniques, especially transmission electron microscope, were used for characterization of these nanoparticles. The phase evolution was further studied using in situ microscopic techniques. After introducing the thesis in the Chapter 1, we describe briefly the relevant literatures in Chapter 2. The experimental details, in particular the experimental set up for laser ablation with targets under liquid are described in chapter 3. This chapter also includes the experimental details of the characterization. Transmission electron microscopy was used as primary characterization tool in the present study. The Chapter 4 presents the result of our study of alloy nanoparticles in Fe-Cu system. This system exhibits a submerged liquid miscibility gap. Although we have studied alloy targets of different compositions, the results of alloy nanoparticles obtained from targets with compositions Cu-40at.%Fe and Cu-60at.%Fe were primarily presented in this chapter. The nanoparticles that were synthesized had a size range of approximately 40nm to more than 100 nm. These particles have spherical morphology. The measurements of local compositions of different locations in the particle indicate the presence of a layer of Fe3O4 oxide at the spherical surface. This layer is devoid of copper. Most of the copper exist in the core of the particle. Fe rich spherical particles of much smaller size (~15 nm) are found to be embedded in the copper rich core. The copper formed solid solution with Fe and a copper concentration gradient exists in the particle below oxide layer due to oxidation of Fe. In contrast the nanoparticles obtained from alloy target with composition Fe-40at.% Cu have a spherical morphology. These have a composite structure with a Fe core in addition to Fe3O4 oxide layer at the surface. We have attempted to explain the phase evolution taking into account under cooling of the melt condensate that forms in the plume and their subsequent solidification through submerged miscibility gap. The chapters 5-7 deals with alloys of Ag-Cu system. In Chapter 5, we have carried out a detailed study of morphological evolution of the nanoparticles of Ag-Cu system. After optimizing the ablation parameters using pure Ag and Cu targets, we have synthesized alloy nanoparticles using different target compositions over the entire range of compositions with sizes having a mode of 25 nm. The evolution of the two phase structure is shown to be composition dependent with particles near equiatomic composition exhibit solid solution with uniformly distributed segregations of composition (Cu & Ag rich) while copper rich alloys exhibit a core shell structure with outer layer being Ag rich. The isothermal experiments again reveal emergence of core-shell morphology at intermediate time for particles with equiatomic composition. In order to compare the results of Ag-Cu nanoparticles with particles produced by other techniques we have synthesized Ag-Cu nanoparticles of near equiatomic composition by chemical route using nitrate salts and NaBH4 as reducing agent. PVP was used as capping agent. The results are presented in chapter 6. Depending on time of reaction, it is possible to synthesis free alloy particles from 2-3 nm to a network of chains. The nanoparticles contain Ag rich and Ag deficient region with Ag tends to segregate near surface. We have also presented mechanism for the formation of chain structure with prolonged reaction. The thermodynamic basis of phase formation in the immiscible system and evolution of phases under nonequilibrium situation have been discussed in chapter 7. This also includes a model to estimate size dependent surface energy. The analysis presented allows a discussion of possible pathways for phase evolution observed in the present work. The thesis ends with a final chapter that discussed the critical issues remains to be addressed and possible future work.