A　novel　series　of　1,2,3-substituted　ferrocene-based　wires　a1–a2　and　b4–b5　have　been　synthesized　by　using　an　iterative　Pd-mediated　Sonogashira　cross-coupling　methodology.　The　molecular　structures　of　a2　and　b3　were　determined　by　single-crystal　X-ray　analysis.　Electrochemical　data　showed　that　there　was　a　strong　electronic　communication　among　the　ferrocenyl　moieties　in　b1–b5.　The　UV　absorption　spectra　indicated　that　replacing　the　1,1′-substituted　ferrocene　unit　with　a　1,2,3-substituted　ferrocene　moiety　causes　delocalization　of　electrons　in　the　extended　π　orbitals.　The　self-assembled　monolayers　of　wire　a1　and　a2　on　Au　surfaces　have　been　comprehensively　characterized　by　electrochemistry　and　scanning　tunneling　microscopy　break　junction.　The　data　demonstrated　that　1,2,3-substituted　ferrocene-based　wires　reduced　the　intermolecular　π–π　stacking,　and　furthermore　solved　the　rotation　problem　in　the　1,1′-substituted　ferrocene-based　wires.　©　2018　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim