New scheelite-based environmentally friendly yellow pigments with the general formula, (BiV)(x)(CaW)(1-x)O-4 (x = 0.2, 0.4, 0.6, and 0.8) have been synthesized by a solid-state route. The resulting colorants were characterized for their structural as well as optical properties. The color parameters, L*, a*, and b* values have been significantly improved in the solid solutions of (BiV)(x)(CaW)(1-x)O-4 over those of BiVO4. Further, the solid solutions allow fine tuning of the optical band gap resulting in various shades of yellow. The synthesized pigments were found to be interesting alternatives to existing toxic yellow pigments.