A commercially available iron compound, [CpFe(CO)2]2 (1) (Cp = η5-C5H5), is an efficient catalyst for the double hydrophosphination of terminal aryl alkynes with diphenylphosphine under visible light irradiation or thermal conditions with a reduction of reaction times of up to two orders of magnitude for some substrates over literature reports. The 1,2-bis(diphenylphosphino)ethane products generated in these reactions are readily isolated in high yields.