Multiferroics have received a great deal of attention because of their fascinating physics of order-parameter cross-couplings and their potential for enabling new device paradigms. Considering the rareness of multiferroic materials, we have been exploring the possibility of artificially imposing ferroelectricity by structurally tailoring antiferromagnets in thin-film forms. YbFeO(3) (YbFO hereafter), a family of centrosymmetric rare-earth orthoferrites, is known to be nonferroelectric (space group Pnma). Here we report that a YbFO thin-film heterostructure fabricated by adopting a hexagonal template surprisingly exhibits nonferroelastic ferroelectricity with the Curie temperature of 470 K. The observed ferroelectricity is further characterized by an extraordinary two-step polarization decay, accompanied by a pronounced magnetocapacitance effect near the lower decay temperature, ~225 K. According to first-principles calculations, the hexagonal P6(3)/mmc-P6(3)mc-P6(3)cm consecutive transitions are primarily responsible for the observed two-step polarization decay, and the ferroelectricity originates from the c-axis-oriented asymmetric Yb 5d(z(2))-O 2p(z) orbital hybridization. Temperature-dependent magnetization curves further reveal an interesting phenomenon of spontaneous magnetization reversal at 83 K, which is attributed to the competition between two distinct magnetocrystalline anisotropy terms, Fe 3d and Yb 4f moments. © 2012 American Chemical Society