SmFeO3, a family of centrosymmetric rare-earth orthoferrites, is known to be nonferroelectric. However, we have found that SmFeO3 is surprisingly ferroelectric at room temperature with a small polarization along the b axis of Pbnm. First-principles calculations indicate that the canted antiferromagnetic ordering with two nonequivalent spin pairs is responsible for this extraordinary polarization and that the reverse Dzyaloshinskii-Moriya interaction dominates over the exchange-striction mechanism in the manifestation of the improper ferroelectricity. SmFeO3 further exhibits an interesting phenomenon of spontaneous magnetization reversal at cryogenic temperatures. This reversal is attributed to the activation of the Sm-spin moment which is antiparallel to the Fe-spin moment below ∼5 K.