Giant magnetostrictive RFe2 type (R represents rare earths) intermetallics form an important class of magnetic materials keeping in view of their potential applications as sensors and/ or actuators. In this thesis, one such mixed rare earth compound (Tb,Dy)Fe2 has been chosen for investigations. Being a technologically important material system, several investigations concerning physical and magnetic properties of the material and effect of processing parameters on magnetic properties have been reported in the available literature. However, existing literature does not provide a clear insight into some important aspects such as phase equilibria, evolution of texture and microstructure of directionally solidified Tb-Dy-Fe alloys. Therefore, the present work was undertaken to bring out tangible process-structure-property correlations with an emphasis to clarify the grey areas in the available literature. The investigation on the nature of ternary phase equilibria of Tb-Dy-Fe was taken up with an aim to understand the effect of Tb/Dy ratio on phase equilibria and magnetic properties of TbxDy1-xFe1.95 (x=0-1) alloys. Microstructural and micro-chemical analysis along with study of lattice parameter has been used to predict the nature of phase equilibria and the deviation from the assumed pseudo-binary behaviour. Further, from the microstructural investigations and study of lattice parameter and Curie temperature, a schematic sketch of a section of the ternary diagram, where (Tb,Dy) / Fe =1.95, was formulated and presented. Directional solidification technique is the most widely adopted method for processing the (Tb,Dy)Fe2, to impart grain orientation for practical applications. Therefore, it was aimed in the present study to understand the evolution of texture and microstructure in directionally solidified Tb0.3Dy0.7Fe1.95 alloy by modified Bridgman and zone melting techniques. The alloy was directionally solidified by modified Bridgman technique with a series of growth rates 5 - 100 cm/h, at a constant temperature gradient of 150oC/ cm. Microstructural investigation revealed formation of island banding at lower growth rate and peritectic coupled growth at higher growth rates. The texture study indicated a transition of growth texture from <113> to <110> and finally to <112> with increase of growth rate. A mechanism based on atomic attachment kinetics is proposed to explain the orientation selection with growth rate. The texture and microstructure have been correlated with magnetostriction and static strain co-efficient (dλ/dH) of the Bridgman solidified alloys. The solidification morphology observed in Bridgman solidified samples was found to be mostly plane front. Therefore, in order to understand the microstructure and texture evolution in cellular/ dendritic regime, directional solidification of Tb0.3Dy0.7Fe1.95 was attempted by zone melting technique with a lesser temperature gradient of 100oC/cm. A detailed texture study indicated a transition in preferred growth direction from <110> to <112> with increase of growth rate. In this case of cellular/ dendritic growth regime, a mechanism based on atomic attachment kinetics has been proposed and the preferred morphologies of the solid-liquid interface for <110> and <112> growth have been modelled. The modelled interfaces have been correlated to the shape of cell/ dendrite cross-section observed for the growth rates adopted in this study. Apart from the investigation carried out on the (Tb,Dy)Fe2 alloys, attempts have been made to understand the role of microstructure, especially the ordered phases on the magnetostriction of an emerging magnetostrictive material Fe-Ga. A series of alloy compositions of Fe-x at % Ga (x=17, 20, 23 and 25) were prepared and subjected to different thermal treatments and characterized for microstructural features and magnetostriction. Microstructure investigation of slow cooled, quenched and quenched + aged alloys reveals formation of ordered DO3 phase from disordered A2 phase by first order transformation in 17 and 20 at% Ga alloys, whereas for 23 and 25 at% alloys, the transformation takes place by continuous ordering. It could be observed that large magnetostriction arises owing to the presence of disordered A2 phase or ordered DO3 phase alone. The magnetostriction however decreases substantially when these two phases are co-existing.