Two　organic-inorganic　hybrid　polyoxovanadoborates　frameworks　were　constructed　using　transition　metal　complexes　(Cd(en)2　2+,　Cu(en)2　2+;　en　=　ethylenediamine)　as　templating　agents　and　open-type　{V12B32}　clusters　as　building　blocks,　forming　2D　layered　architectures.　The　O-HO　hydrogen　bonds　between　the　clusters　link　the　layers　to　form　a　3D　supramolecular　structure.　Single-crystal　analysis　and　two-dimensional　correlation　infrared　spectroscopy　(2D-COS-IR)　revealed　that　the　two　isostructural　compounds　exhibit　distinct　hydrogen-bonding　patterns,　channel　dimensions,　and　porosity　due　to　differences　in　the　coordinated　transition　metal　ions,　ultimately　leading　to　variations　in　solvent　molecule　content.　The　compounds　exhibit　proton　conduction　properties　with　a　conductivity　of　9.52　x　10-4　Scm-1　for　1　and　1.93　x　10-2　S　cm-1　for　2　at　85　degrees　C　and　98%　RH.　The　enhanced　proton　conduction　in　2　directly　correlates　with　its　larger　channel　dimensions,　which　facilitate　more　efficient　proton　transport　pathways.