To explore the effect of filler on the electrical conductivity of polymer nanocomposites, polystyrene coacrylonitrile and TiO 2 (PSAN/TiO 2 ) nanocomposites of different TiO 2 wt% have been prepared. The microstructural characterization has been performed by positron annihilation lifetime spectroscopy (PALS). Positron lifetime parameters viz. o-Ps lifetime (s 3 ) and free volume size (V f ) decreases up to 0.6 wt% suggests the filling of the cavities by Ti 31 and O 2 ions as well as complex formation. The increased free volume size (V f ) after 0.6 wt% of TiO 2 was attributed to the o-Ps annihilation at the interface of PSAN and TiO 2 nanoclusters. The variation of electrical conductivity at lower and higher concentration of TiO 2 is attributed to the blocking effect and space charge effect, respectively. The electrical conductivity decreases along with the free volume sizes at lower concentration of TiO 2 due to the hindrance of the ions mobility. The increased conductivity with the increased free volume sizes indicates the formation of more void space at the interface due to the formation of TiO 2 nanoclusters. The surface morphology of the nanocomposites studied by scanning electron microscopy (SEM) shows uniform dispersion at the lower wt% of TiO 2 and increased size of nanocluster formation at the higher concentration of TiO 2 nanoparticles in PSAN matrix. The crystallinity evaluated by X-ray diffraction (XRD) results also indicates the formation of TiO 2 nanoclusters between 0.6 and 1.0 wt% of TiO 2 . Fourier transform infrared spectroscopy (FTIR) suggests the improved chemical and physical interaction between the functional groups of TiO 2 and polymer side chain. POLYM. COMPOS., 00:000-000,