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A new hybrid material was created by blending sodium titanate ceramics (Na2Ti3O7/Na2Ti6O13) with a polyvinyl alcohol (PVA) matrix, resulting in enhanced semiconductive characteristics. The synthesis process involved intense ultrasonic treatment and subsequent heat treatment at 900 °C. Utilizing a solvent casting method, Na2Ti3O7/Na2Ti6O13/PVA composites were fabricated. Raman spectra confirmed the presence of PVA chains and distinctive bands of sodium titanates. Elemental analysis verified the existence of Na and Ti in both composites. Morphological observations revealed the formation of irregular agglomerates upon introducing sodium titanates into the PVA structure, leading to a rise in the average surface roughness (Ra) from ~ 1.5 to 7.9 nm post-incorporation of heated Na2Ti3O7/Na2Ti6O13. Differences in morphology between samples loaded with unheated and heated Na2Ti3O7/Na2Ti6O13 suggested a more effective particle incorporation into the polymeric matrix after heat treatment. Electrical measurements indicated that the composite loaded with unheated Na2Ti3O7/Na2Ti6O13 exhibited the lowest electrical resistance (105 Ω) and a relaxation time of 3.16 × 10− 5 s. These results demonstrate that the inclusion of sodium titanate ceramics enhances the semiconductive properties of the PVA matrix. This finding highlights the potential of this material for various electronic applications, including components for solid-state batteries. [ABSTRACT FROM AUTHOR]