A　reaction　of　acetonitrile-solvated　AgOCF3　with　1　equiv.　of　Aryl-BIAN　ligand　in　THF　at　room-temperature　afforded　the　silver(i)　complex　(Aryl-BIAN)AgOCF3　(1)　in　75%　yield.　The　crystal　structure　of　this　silver(i)　trifluoromethoxide　was　determined　by　single-crystal　X-ray　crystallography.　The　molecular　structure　of　1　shows　the　metal　centre　bound　to　one　molecule　of　BIAN,　one　trifluoromethoxide　and　one　THF　solvate,　resulting　in　a　distorted　tetrahedral　silver.　Density　functional　theory　(DFT)　calculations　and　the　natural　bond　orbital　(NBO)　analysis　were　conducted　to　give　insights　into　the　electronic　structure　of　1　and　the　bonding　characters　of　the　OCF3　group.　The　reactivity　of　1　towards　trifluoromethoxylation　of　organic　halides　was　also　examined;　a　reaction　with　benzyl　bromides　gave　the　desired　products　of　benzyl　trifluoromethyl　ethers　in　good　to　excellent　yields.　©　The　Royal　Society　of　Chemistry.