The presence of tetragonal distortion and spontaneous polarisation in lead titanate attracts the researchers to modify the titanate perovskites. A modified lead titanate Pb(Cd1/3W1/3Ti1/3)O3 perovskite is synthesised by a conventional high-temperature solid-state reaction technique. XRD pattern of the sample confirms the cubic crystal structure having space group F-43m. Full proof Rietveld analysis has been used for structural refinement. The presence of FTIR frequency bands corresponding to Ti-O, O-, W-O-W, and CdO stretching confirm that Cd2+, W6+ ions completely substitute the Ti+4 ions at the B site of the perovskite, as confirmed by the XRD obtained data. As the frequency increases from 1 kHz to 5 MHz, the activation energy (Ea) decreases from 0.767 eV to 0.089 eV. The activation energy and conductivity mechanism in the samples dominated by hopping charge carriers. Both Nyquist and Cole-Cole plots confirm the semiconducting nature of the samples and make the material technologically important.