We report optical enhancement in polarization and dielectric constant near room temperature in Pb_0.6Li_0.2Bi_0.2Zr_0.2Ti_0.8O₃ (PLBZT) electro-ceramics; these are doubly substituted members of the most important commercial ferroelectric PbZr_0.2Ti_0.8O₃ (PZT:20/80). Partial (40%) substitution of equal amounts of Li⁺¹ and Bi⁺³ in PZT: 20/80 retains the PZT tetragonal structure with space group P4 mm. Under illumination of white light and weak 405 nm near-ultraviolet laser light (30 mW), an unexpectedly large (200-300%) change in polarization and displacement current was observed. Light also changes the dc conduction current density by one to two orders of magnitude with a large switchable open circuit voltage (V_ocv ∼ 2 V) and short circuit current (J_scc∼ 5 × 10⁻⁸ A). The samples show a photo-current ON/OFF ratio of order 6:1 under illumination of weak light.