The proper functionalization of nickel bis(dithiolene) complexes by pendant cholesteryl fragments allows for the formation of extended networks of intertwined fibers providing robust gels. Furthermore, such nickel bis(dithiolene) complexes are also efficient photothermal centers in solution in the near infrared (NIR), with a photothermal conversion efficiency comparable to that of gold nanoparticles. This unprecedented association in one single molecule, of the two properties, i.e., gelation ability and photothermal effect, gives a highly efficient handle to modulate the gel stability through light irradiation in the NIR region, providing a novel approach to photoresponsive gels.