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 BP0.95V0,05O4 and BP0.9V0.1O4 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 absorptioh edge values were found to be around 569 and 591 nm in the case of BP0.95V0.05O4 and BP0.9V0.1O4 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. (C) 2017 Elsevier Ltd. All rights reserved.