The purpose of this work was to investigate olefin/silver (I) complexation and transport through silver facilitated transport membranes. Specifically, the transport of 1,5-hexadiene and of 1-hexene within these membranes was studied and a hypothetical conformation for the silver (I) complex of 1,5-hexadiene in aqueous systems is discussed. Absorption of 1-hexene and 1,5-hexadiene into aqueous silver nitrate solutions revealed predominantly 1:1 complexation of these olefins with silver. Absorption and transport experiments in silver-exchanged Neosepta (R) CM-1 membranes confirmed the predominance of 1:1 1,5-hexadiene/silver (I) complexation in this membrane as well, showing that transport through these membranes occurs primarily through a 1:1 1,5-hexadiene/silver (1) complexation mechanism.