The hydroformylation of vinyl acetate was carried out using rhodium complex of naphthyl-based monodentate bulky phosphine and phosphite ligands. All the naphthyl-based ligands favored the formation of desire branched aldehyde. High turnover frequency with excellent regioselectivity to branched aldehyde and high selectivity to aldehyde were observed with bulky phosphite ligands. The effect of partial pressure of CO and H-2, concentration of vinyl acetate, stirring rate and solvents on the hydroformylation of vinyl acetate catalyzed by Rh/bulky phosphite were examined precisely in order to improve the catalytic activity and selectivity. In contrast to conventional organic solvents, the significant influence on the activity and selectivity was observed in organic carbonates ('green' solvent) particularly in propylene carbonate (PC). The PC/catalyst system could be recycled without significant loss of activity and selectivity. (C) 2012 Elsevier B.V. All rights reserved.