Here,　α-　or　β-thiophene-substituted　derivatives　bridged　by　an　o-carborane　group　were　synthesized.　Scanning　tunneling　microscope　break　junction　techniques　have　revealed　that　the　thiophene　anchoring　groups　form　a　single-molecule　junction　with　an　Au　electrode.　Flicker　noise　analysis　suggests　the　existence　of　through-space　transmission　pathways　between　the　thiophene　units.　Furthermore,　the　electronic　coupling　of　the　β-thiophene　substituted　molecule　with　the　electrode　is　found　to　be　more　stable,　resulting　in　a　70　%　increase　in　conductance　compared　to　the　α-isomer　counterpart.These　findings　offer　valuable　insights　for　the　design　and　development　of　o-carborane-based　molecules,　underscoring　the　significance　of　molecular　backbones　and　substitution　patterns　on　their　electrical　transport　properties.　©　2024