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Hexagonal rare-earth ferrite RFeO₃ family is a unique multiferroic material holding weak ferromagnetic moment, which is predicted to be coupled with trimerization. Until now, only the low temperature magnetic transitions at 120~170 K have been verified. We stabilize this structure in YbFeO₃ with finely tuned Sc substitution level, and demonstrate a new near room-temperature magnetic ordering at T_c ~ 225 K in Yb_0.42Sc_0.58FeO₃, accompanying the ferroelectric transition. The weak ferromagnetism is also unambiguously evidenced below T_c, which is originated from the magnetoelectric spin-lattice coupling. More importantly, three successive magnetic transitions at T_R1 ~ 165 K, T_R2 ~ 33 K and T^* ~ 8.5 K have been observed, which may indicate complex interaction between the rare-earth and Fe ions magnetic moments. The present work pushes forward the progress to hunt for room-temperature multiferroics in hexagonal ferrites and related materials.