We present two surface-immobilization schemes that connect an azurin variant with mutations in the redox cavity to two oligophenylvinyl (OPV) molecular wires, along with an electrochemical study of their electron transfer (ET) properties. OPV embedded within alkanethiol films tether selectively the azurin mutants from solution and further connect them onto electrodes, as does protein reconstitution with OPV in solution followed by complex adsorption. Stable cyclic voltammograms are measured in either scenario, with highest ET values (k0 approximate to 740 s(-1)) comparable to those observed for the gold-adsorbed native azurin (k0 approximate to 400 s(-1)). Furthermore, subtle structural differences between the structurally-analogous OPV allow for the investigation of the optimal electronic conduit between the redox center and supporting gold electrodes (1.6-1.7 fold difference). (C) 2017 Elsevier B.V. All rights reserved.