The possible multifunctional characteristics of spin cycloid arranged LaFeO3(LFO) modified BaTiO3(BTO) solid solution, derived through the traditional solid reaction route have been investigated and reported here. The XRD (X-Ray Diffraction) refinement through POWD (Powdered Diffraction) and MAUD (Material Analysis Using Diffraction) revealed the crystal structure as tetragonal belonging to the P4mm space group. SEM–EDS spectroscopy was engaged to probe the sample surface morphology and the presence of the desired elements. The dielectric spectroscopic investigation at some discrete temperature intervals reveals the compound’s good dielectric response at a lower frequency. The complex \(Z\left( \omega \right)\) IS and \(M\left( \omega \right)\) analysis outcomes advocate thermally agitated relaxation, capacitive, and NTCR (Negative Temperature Co-efficient of Resistance) behavior. The existence of various vibrational modes was investigated via Fourier Transform IR (FTIR) characterization. The UV analysis revealed the sample’s excellent photovoltaic response and potential photoelectronic device fabricability. The M-H loop investigation revealed substantial ferromagnetic ordering along with an antiferromagnetic competitive factor.