Blended polymer films of polyethylene oxide + polyvinyl pyrrolidone (PEO + PVP) containing transition metal (TM) ions like Fe³⁺, Co²⁺ and Ni²⁺ have been synthesized by a solution casting method. For these films, structural, thermal, magnetic and optical properties have been studied. X-ray diffraction results reveal the semi-crystalline nature of the polymer films. Thermal stability of the host (undoped) polymer film has been investigated from its thermogravimetric–differential thermal analysis profiles. Raman spectral profiles indicate a complex formation trend owing to the addition of TM ions into the host matrix. Co²⁺, Fe³⁺ and Ni²⁺ ions doped polymer films have revealed ferromagnetism based on their vibrating sample magnetometre profiles. However, the host polymer film has exhibited a paramagnetic nature. Further, ionic conductivities have been calculated using an impedance analyser at different temperatures for all the samples. Among these films, a maximum ionic conductivity (𝜎 = 7.5 × 10⁻⁶ S cm⁻¹) has been noticed from PEO + PVP : Ni²⁺ polymer film at 373 K. Emission analysis of Co²⁺ : PEO + PVP polymer film has exhibited a strong red emission under an UV source and from both PEO + PVP : Fe³⁺; PEO + PVP: Ni²⁺, green emissions have commonly been noticed under an UV source. Thus, based on these results, it could be suggested that these TM ions doped PEO + PVP polymer films are found to be potential multifunctional materials for magneto-electric, magneto-optic fields with encouraging electrical, dielectric and optical properties as well as displaying with ferromagnetic nature from the doped films.