Although attaching methylthio (-SMe) to the ortha-position of thiophene/furan to produce a new linker motif has been employed for extending the variety of molecular conductance measurements, the atomic-scale details of the attachment to electrodes remain ob-scure, which is not conducive to precisely interpreting the transport mechanism of a molecule terminated by such anchors. To address this issue accordingly, we combined experimental conductance investigations and theoretical molecular simulations, which demon-strates that both thiophene and furan benefiting from -SMe providing additional binding strength are upgraded as bidentate anchors, as evidenced by the increased junction formation probability and their enhanced electrical properties for the -SMe modified molecule. This work thus provides a clear insight of 2-(methylthio)thiophene/furan binding to the Au electrodes, paving the way for their further applications in molecular electronics.