A novel class of luminescent phosphole oxide-containing alkynylgold(III) complex has been synthesized, characterized, and applied as active material in the fabrication of solution-processable resistive memory devices. Incorporation of the phosphole oxide moiety in gold(III) system has been demonstrated to provide an extra charge-trapping site, giving rise to intriguing ternary memory performances with distinct and low switching threshold voltages, high OFF/ON1/ON2 current ratio of 1/10(3)/10(7), and long retention time for the three states. The present study offers vital insights for the future development of multilevel memory devices using small molecule organometallic compounds.