We report on the light-induced switching of conductance of a new generation of diarylethene switches embedded in an insulating matrix of dodecanethiol on Au(111), by using scanning tunneling microscopy (STM). The diarylethene switches we synthesize and study are modified diarylethenes where the thiophene unit at one side of the molecular backbone introduces an intrinsic asymmetry into the switch, which is expected to influence its photo-conductance properties. We show that reversible conversion between two distinguishable conductance states can be controlled via photoisomerisation of the switches by using alternative irradiation with UV (λ = 313 nm) or visible (λ > 420 nm) light. We addressed this phenomenon by using STM in ambient conditions, based on switching of the apparent height of the molecules which convert from 4–6 Å in their closed form to 0–1 Å in their open form. Furthermore, the levels of the frontier molecular orbital levels (HOMO and LUMO) were evaluated for these asymmetric switches by using Scanning Tunneling Spectroscopy at 77 K, which allowed us to determine a HOMO–LUMO energy gap of 2.24 eV.