A single-pot, wet chemical method has been reported for the synthesis of bismuth fluoride nanoparticles (BF) and functionalized BF within the network of carbon nitride (BFCN). In BFCN, a structural transformation of BF, from cubic to pseudo-cubic (as evidenced by Rietveld refinement analysis), confirmed the contribution of carbon nitride (CN) on functionalization. The effect of functionalization of BF has been investigated through dielectric and field-induced polarization studies under different temperature and frequency conditions. Enhancement of dielectric constant values was noticed in BFCN as compared with BF system, in the order of 2.5 (30 °C) and 8.0 (100 °C) at 100 Hz. Fatigue-free maximum polarization values of 0.041 µC/cm2 and 0.054 µC/cm2, under the electric field of 5 kV/mm, were achieved for BF and BFCN samples, respectively, for 5 × 103 cycles.