The homogeneous hydroformylation of pent-4-enal, the preferred aldehyde intermediate from 1,3-butadiene hydroformylation, was systematically investigated with Rh catalyst complexes in neat and CO2-expanded toluene media at 40-80 degrees C, syngas partial pressures ranging from 5-50 bar, and different ligand/Rh ratios. At similar operating conditions, the TOFs are generally greater with Rh/DIOP relative to a Rh/TPP catalyst. On both catalyst complexes, the chemoselectivity toward the dialdehydes ranges from 75%-100%, with the maximum adipaldehyde selectivity reaching approximately 75% (n/i similar to 3) at 60 degrees C, 10 bar syngas, and molar DIOP/Rh ratio of 2.5. By using CO2-expanded toluene, the regioselectivity toward the adipaldehyde (desired product), and therefore its yield, is significantly enhanced. Interestingly, even with the simple Rh/TPP catalyst complex, adipaldehyde selectivity of up to 85% (n/i similar to 5.6) is achieved at 60 degrees C, 10 bar syngas, and 50 bar CO2. The beneficial effects of CO2-expanded media are attributed to the facile tunability of the H-2/CO ratio in such a phase with a fixed syngas feed composition. This approach to accelerate pent-4-enal hydroformylation to form adipaldehyde could also help in overcoming equilibrium limitations typically associated with the catalytic isomerization of pent-3-enal (the dominant product from 1,3-butadiene hydroformylation) to pent-4-enal (the preferred isomer).