This work focuses on developing flexible nanocomposites by introducing two types of ceramic nanofillers into a biopolymeric blend for optoelectronic and energy-storing applications. Selenium oxide (SeO2) nanoparticles (NPs) and LaFeO3 NPs were prepared by hydrothermal and solid-state reactions, respectively, and incorporated into the polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) through the solution casting process. Transmission electron microscope and X-ray diffraction tests revealed the creation of hexagonal SeO2 and orthorhombic LaFeO3 NPs, with average sizes of 17 and 93 nm. The blend's degree of crystallinity was dependent on SeO2 NPs and LaFeO3 contents. The infrared absorption spectra revealed the interactions/complexation of the fillers with the blend reactive groups. The scan e-microscope (field emission mode) investigated the films' surface morphology and detected the elements they contain. LaFeO3/SeO2 content impacted stress-strain behavior, raised the tensile strength from 64 to 70.9 MPa, and dramatically lowered the strain at break and toughness. UV–vis-NIR measurements exhibited that the transmittance, extinction coefficient, and refractive index can be tuned by SeO2 and LaFeO3/SeO2 content. The direct (Eg.d)/indirect (Eg.id) band gaps were reduced from 5.25/4.9 eV to 4.95/4.7 eV. The dielectric parameters (constant, loss, energy density, and conductivity) were significantly increased after loading 5.0 wt% LaFeO3/SeO2. The dielectric moduli and Cole-Cole plots were also investigated. The structural modifications and enhancement of the optical features and dielectric parameters make the resulted samples the best candidates for optoelectronic devices and energy-storing applications such as sensors and supercapacitors.