Polyethylene glycol based diphosphinite ligands and their Wilkinson type Rh-polymeric carbonyl complexes were prepared for homogeneous hydroformylation of styrenes. The effect of reaction variables such as temperature, pressure, P/Rh ratio, Substrate/Rh ratio, phosphine and phosphinite ligands on the activity and selectivity performance were discussed in detail. The catalyst showed a high rate of reaction, TON and tunable regioselectivity depending upon reaction conditions as compared to conventional Rh-phosphine based catalysts.