Intercalation of HRh(CO)(TPPTS)(3) complex into the interlayer space of hydrotalcite was carried out to prepare an eco-friendly heterogeneous hydroformylation catalyst. Intercalated catalyst was characterized by P-31 NMR, P-XRD, FT-IR. SEM and surface area measurements. Catalytic activity of intercalated catalyst [HT(3.5)-INT] was evaluated for hydroformylation of linear alkenes of varied carbon number from C-5 to C-13 as well as cyclic alkenes. Selectivity of the aldehydes was observed to decrease with increase in the carbon chain length of linear alkenes. Effect of reaction parameters on catalytic activity of intercalated catalyst was studied by varying the catalyst amount, 1-hexene concentration. reaction temperature, partial pressure of carbon monoxide and hydrogen for hydroformylation of 1-hexene. The catalyst was re-cycled up to five times without significant loss in the alkene conversion and selectivity of aldehydes. (C) 2009 Elsevier B.V. All rights reserved.