Recent STM molecular break-junction experiments have revealed multiple series of peaks in the conductance histograms of alkanedithiols. To resolve a current controversy, we present here an in-depth study of charge transport properties of Au vertical bar alkanedithiol vertical bar Au junctions. Conductance histograms extracted from our STM measurements unambiguously confirm features showing more than one set of junction configurations. On the basis of quantum chemistry calculations, we propose that certain combinations of different sulfur-gold couplings and trans/gauche conformations act as the driving agents. The present study may have implications for experimental methodology: whenever conductances of different junction conformations are not statistically independent, the conductance histogram technique can exhibit a single series only, even though a much larger abundance of microscopic realizations exists.