Nanocrystalline pure and Gd3+ doped CoWO4 nanostructures were synthesized by single step chemical precipitation technique. The framework substitution of Gd in CoWO4 nanoparticles was established by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) techniques. XRD pattern reveals the pure and doped CoWO4 nanoparticles belong to the monoclinic structure. The increase in Gd doping enhanced the ‘blue-shift’ in the UV-Vis absorption spectra. Electron microscopy studies clearly evidence the formation of round edged nanocubes with an average particle size of 60–80 nm, emerges in the polycrystalline nature. UV–Visible absorption spectra of Gd doped CoWO4 nanocrystals shows a strong absorption peak at 278nm. Nonlinear optical transmission studies of the nanocomposites is measured using the open aperture Z-scan technique employing 7 nanosecond laser pulses at 532 nm. Experimental results show that both pure CoWO4 and Gd doped nanoparticles exhibit excellent optical limiting performance.