Polyurethane (PU)–perovskite nanocomposite films were developed by in situ addition of nickel titanate nanoparticles (NiTiO₃ NPs) into a PU matrix formulation. Among the three samples of NiTiO₃ NPs calcinated at 400, 600 and 800 °C, the pertinent rhombohedral phase of NiTiO₃ has been achieved at 800 °C. NiTiO₃ is loaded in trace amounts (0.5 wt%) with the PU matrix to cast as films (thickness ∼ 1.5 mm), which demonstrate its influence on PU, studied by ATR-IR, Raman, UV-vis DRS, XRD, TGA, DSC, XPS, AFM, SEM, optical microscopy, vibrating sample magnetometer (VSM) and impedance spectroscopy. The characteristics of the PU–NiTiO₃ nanocomposite films are compared with a control PU film, and these reveal the enhancement in thermal stability (>10 °C), electrical conductivity (8.72 × 10⁻⁵ S cm⁻¹) and mechanical strength (19.7 ± 0.8 MPa) as well as the effect on magnetic and optical properties due to non-covalent interactions upon uniform distribution of NiTiO₃ on the PU film.