We present here the experimental results of BiFe0.75Cr0.25O3 (BFCO) thin film deposited by sol–gel spin coating technique directly on Pt(111)/Ti/SiO2/Si substrate at different thicknesses. The crystal structure of BFCO has been investigated using X-ray diffraction which acts as a double perovskite structure with high crystallinity obtained at 400 °C. Further microscopic studies such as scanning electron microscope (SEM) with EDAX, transmission electron microscope (TEM) were also used in identifying the grain size and particle distribution over Pt (111) substrate. Atomic force microscopy (AFM) on the films at a different thickness (− 80 to − 250 nm) reveals that the surface roughness and other amplitude parameters increases with the increase in thickness signifying an increase of grain size with thickness. Increase in grain size and substrate clamping effect between the BFCO film and the substrate induces change in ferroelectric polarization and dielectric properties in relation to thickness effect. Similarly, decrease in magnetization from 9.241 emu/cm3 (− 80 nm) to 5.7791 emu/cm3 (− 250 nm) is attributed to the formation of anti-sites and anti-phase boundaries in the films. In addition, temperature dependence of magnetization reveals ferromagnetic super-exchange interaction of BFCO which is unlike the spin structure of antiferromagnetic BiFeO3.