Orthorhombic perovskite type LnVO3 and Ln1-xTVO 3 (Ln = Ce, Pr, and Nd) have been synthesized by the solid state method. The structures of these compounds have been unequivocally established based on high resolution powder X-ray diffraction data using Rietveld refinement methodology followed by difference Fourier analysis. It is shown that substitution of Ti occurs at the vanadium site and not at the cerium site. The compounds have been tested for photocatalytic degradation of various dyes and substituted phenols. It is observed that doping of Ti remarkably improves the photodegradation efficiency of these orthorhombic perovskites. © 2009 American Chemical Society.