We investigate the structural evolution of PtRu and CoRh ultra fine bimetallic particles as a function of their composition in the whole range of stoichiometry. Isolated particles embedded in an organic matrix are synthesized using chemical techniques in mild conditions. Their size, dispersion and structure are analyzed by HRTEM, WAXS and EXAFS techniques. The magnetic behavior of cobalt-based alloys is investigated by SQUID magnetometry. In the PtRu alloys, we demonstrate the role of composition in the structural transition from the face-centered cubic to the hexagonal close packed structure in nanoparticles and detail the mechanism of the transition. We point out the effect of size reduction and core-shell atomic distribution in the structure and the enhanced magnetization in CoRh bimetallic particles.