This article documents the unexpected optical property observed in chemically modified BPO₄ which is carried out by partial substitution of P⁵⁺ ion by V⁵⁺ ion and redox behaviour of the resultant new phases. Structurally, the extent of bigger V⁵⁺ ion substitution for smaller P⁵⁺ ion in the phosphate lattice is found to be restricted. Powder X-Ray diffraction and FT-IR analysis confirmed BP_0.95V_0.05O₄ and BP_0.9V_0.1O₄ as optimized compositions and were further characterized by UV-VIS-NIR and SEM-EDS techniques. Nevertheless, such small replacement of PO₄ moiety by VO₄ moiety in BPO₄ lattice resulted in greatly enhanced optical absorption and the absorption edge values were found to be around 569 and 591 nm in the case of BP_0.95V_0.05O₄ and BP_0.9V_0.1O₄ respectively against the absence of such absorption in the parent BPO₄. In addition, the new phosphovanadates exhibited redox behaviour on interacting with hydrazine and hydrogen peroxide.