Basic stellar atmospheric parameters, such as effective temperature, surface gravity, and metallicity plays a vital role in the characterization of various stellar populations in the Milky Way. The Stellar parameters can be measured by adopting one or more observational techniques, such as spectroscopy, photometry, interferometry, etc. Finding new and innovative ways to combine these observational data to derive reliable stellar parameters and to use them to characterize some of the stellar populations in our galaxy is the main goal of this thesis. Our initial work, based on the spectroscopic and photometric data available in literature, had the objective of calibrating the stellar parameters from a range of available flux observations from far-UV to far-IR. Much effort has been made to estimate probability distributions of the stellar parameters using Bayesian inference, rather than point estimates. We applied these techniques to blue straggler stars (BSSs) in the galactic field, which are thought to be a product of mass transfer mechanism associated with binary stars. Using photometry available in SDSS and GALEX surveys we identified 85 stars with UV excess in their spectral energy distribution (SED) : indication of a hot white dwarf companion to BSS. To determine the parameter distributions (mass, temperature and age) of the WD companions, we developed algorithms that could fit binary model atmospheres to the observed SED. The WD mass distribution peaks at 0.4M , suggests the primary formation channel of field BSSs is Case-B mass transfer, i.e. when the donor star is in red giant phase of its evolution. Based on stellar evolutionary models, we estimate the lower limit of binary mass transfer efficiency β ~ 0.5. Next, we have focused on the Canis Major overdensity (CMO), a substructure located at low galactic latitude in the Milky Way, where the interstellar reddening (E(B-V )) due to dust is significantly high. In this study we estimated the reddening, metallicity distribution and kinematics of the CMO using a sample of red clump (RC) stars. The averageE(B-V)(~0.19)is consistent with that measured from Schlegel maps (Schlegal et.al. 1998). The overall metallicity and kinematic distribution is in agreement with the previous estimates of the disk stars. But the measured mean alpha element abundance is relatively larger with respect to the expected value for disk stars.