Rhodium complexes of the type HRh(CO)L₃ (where L is an N-pyrrolyl phosphine, such as P(NC₄H₄)₃, PPh(NC₄H₄)₂, or PPh₂(NC₄H₄)) were applied in the hydroformylation of less reactive unsaturated substrates, namely allyl acetate, butyl acrylate, methyl acrylate, 2,3-dihydrofuran and vinyl acetate. Even at room temperature, these catalysts enabled complete substrate conversion and high chemoselectivity towards the corresponding aldehydes. High conversion of vinyl acetate (88% in 6 h) to the branched aldehyde was obtained with HRh(CO)[P(NC₄H₄)₃]₃ at 25 °C. An increase of the turnover frequency, TOF, up to 2000 mol mol⁻¹ h⁻¹ was achieved in this reaction under 20 bar of syngas (H₂/CO = 1) at 80 °C. The introduction of chiral phosphines, BINAP or Ph-BPE, to this system resulted in the production of a branched aldehyde with enantioselectivity, ee, up to 44 and 81%, respectively. High activity combined with high enantioselectivity was achieved due to the formation of the mixed rhodium hydrides HRh(CO)[P(NC₄H₄)₃](BINAP) and HRh(CO)[P(NC₄H₄)₃](Ph-BPE), identified by the NMR method.