PVP capped with (Cu2+, Mn2+) codoped CdS and undoped nanoparticles were prepared by chemical precipitation method. The XRD patterns revealed that codoped CdS nanoparticles exhibit in cubic hawleyite mixed with hexagonal greenockite phase. The functional groups of the capping agent on codoped CdS surface were identified by FTIR. The UV–visible absorption spectra show significantl blue shift (501–514nm) and second excitonic absorption peak 241nm was observed only in the presence of a narrow size distribution. The increased optical band gap confirms the presence of quantum confinement. The photoluminescence (PL) emission spectrum shows emission line in the blue region. The emission band reveals that the measured band gap of around 2.7eV is greater than that of bulk CdS (2.42eV).T The average g–value, total number of spins (Ns) and covalency parameter (α2) were calculated from EPR results. The Cyclic Voltammetry curve of cathodic and anodic peaks shifted slightly to negative and positive potentials, respectively for electrode applications.