Nanoparticulate thin films of GaAs we electrochemically prepared from acidic solutions of pure metallic Ga and As2O3. Samples of different crystallite sizes were prepared by varying the electrolysis parameters. Structural characterization of the nanoparticles were carried out by XRD technique which exhibits partial amorphization of the crystallites in the low electrolysis current regime. Quantum confinement effect was prominently observed in the optical absorption spectra with blueshift of absorption onsets with respect to the bulk band gap. Room temperature photoluminescence exhibit band edge luminescence as well as other surface related bands. Incorporation of transition element as impurity leads to enhanced luminescence intensity and generates deep traps.