This work presents a detailed study on the preparation and performance of polyaniline (PANI)/Polyvinyl alcohol (PVA) blend. The blends are prepared by the casting method at different weight ratios (1, 2, 3, 4, and 5 wt%). The structural morphology was characterized using scanning electron microscope SEM. The morphological analysis showed a uniform blend of PANI with PVA matrix. PVA exhibits lamellae structure of different shapes and dimensions. For 1% PANI, the results showed homogeneous blending, which decreases with an increase of the PANI ratio. Phase separation and semispherical region formation in the PVA matrix were seen. It was found that incompatibilities increase with increasing the PANI ratio. Also, the results proved in the blends scanning electron microscope anilinium cationradical surfaces for an aggregate of different dimension and spherical shapes, which induced by surface tension. The electrical conductivity study of PANI/PVA blends and PVA reveals that PANI/PVA gives the conductivity of 10 −4 (cm.Ω) -1 , while PVA presented the lowest conductivity with the value of 10 −12 (cm.Ω) -1 . The results also showed an increase in ionic conductivity with temperature and PANI weight ratio. The increase in electrical conduction with increasing temperatures is due to the negative thermal coefficient, this result is attributed to the polymer chains that act as traps for charge carriers, and when the temperature rises, the transfer mechanism will be reigned by the hopping process.