Trialkyphosphine oxides (TRPO) was successfully used for the impregnation of D3520 resin to prepare an extractant-impregnated resin (EIR). Solid extraction of Au(Ⅰ) from alkaline cyanide solution was studied using this extractant-impregnated resin (EIR), with addition of cetyltrimethylammonium bromide (CTMAB), directly into the aurous aqueous phase in advance. The mechanism of solid extraction was further investigated by means of FTIR, XPS and SEM. The column separation studies have shown that cationic surfactant CTMAB played a key role in the solid phase extraction, and the resin containing TRPO were effective for the extraction of gold when the molar ratio of CTMAB:Au(Ⅰ) reached 1:1. FTIR spectroscopy of gold loaded EIR showed that the frequency of C≡N stretching vibration was at 2　144 cm-1, and the frequency of PO stretching vibration shifted to lower frequency from 1　153 to 1　150　cm-1. The XPS spectrum of N(1s)， Au(4f7/2) and Au(4f5/2) suggested that the coordination environment of gold did not change before and after extraction, and gold was still as the form of Au(CN)-2 anion exiting in the loaded resin; O(1s) spectrum showed that the chemically combined water significantly increased after solid extraction from 30.74% to 42.34%; Comparing to the P(2p) spectrum before and after extraction, the binding energy increased from 132.15 to 132.45　eV, indicating there maybe existing hydrogen-bond interaction between PO and water molecule, such as P=O…H—O—H. The above results obtained established that in the solid extraction process, the hydrophobic ion association ［CTMA+·Au(CN)-2］ diffused from the bulk solution into the pores of the EIR, and then be solvated by TRPO adsorbed in the pores through hydrogen bonding bridged by the water molecules.