Rare-earth orthochromites, RCrO 3 (R = rare-earth and Y) with magnetic R-ions are reported to exhibit ferroelectricity at the magnetic ordering temperature of Cr 3+-ions (Rajeswaran, B.; Khomskii, D. I.; Zvezdin, A. K.; Sundaresan, A.; Rao, C. N. R. arXiv2012, 1201, 0826v1). Interestingly, we observe ferroelectricity at the Néel temperature of orthochromites containing a nonmagnetic R-ion (Y) upon introducing cation-disorder at the Cr-site by incorporation of another magnetic ion of nonequivalent spin. For example, the weakly ferromagnetic perovskite, YCr 0.5Fe 0.5O 3, where the Cr 3+ (S = 3/2) and Fe 3+ (S = 5/2) ions at the B-site are disordered, exhibits ferroelectricity at T N = 260 K. Ferroelectricity is observed not only when the relative proportions of Fe 3+ and Cr 3+ ions as in YCr 1-xFe xO 3 are varied but also when Y 3+ ions are replaced by other nonmagnetic R-ion and the transition metal ions changed as in YCr 1-xMn xO 3. While the local polarization cancels out in the weakly ferromagnetic YMO 3 (M = Cr and Fe), a nonzero polarization in these materials seem to arise due to disordered transition metal ions of nonequivalent spins. © 2012 American Chemical Society.