Diphosphino-functionalized MCM-41-immobilized rhodium complex (MCM-41-2P-RhCl3) was conveniently synthesized from commercially available and cheap gamma-aminopropyltriethoxysilane via immobilization on mesoporous MCM-41, followed by reacting with diphenylphosphinomethanol and rhodium chloride. It was found that this heterogeneous rhodium complex is a highly efficient catalyst for the hydrophosphinylation of terminal alkynes with diphenylphosphine oxide and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity. Hydrophosphinylation of terminal alkynes using diphosphino-functionalized MCM-41-immobilized rhodium complex (MCM-41-2P-RhCl3) as an efficient heterogeneous catalyst is described. This heterogeneous rhodium complex is highly active catalyst and can be reused at least 10 times without any decrease in activity.