Synthesis of intermetallic PbSe induced by high-energy ball milling has been studied. Systematic analysis of transformation in the resulting phases of milling from 0 to 10 h has been traced by characterizing the microstructures in terms of morphology, crystallite size, and percentages of phases formed as a function of milling time. Results reveal the formation of two phases. Where the system of PbO-Se transforms gradually to PbSe. Complete transformation is achieved after 10 h of milling time. Study of particle structure by the Rietveld Method further corroborates the value of the nano-order crystallite diameters as evaluated from the microscopic studies.