Porphyrins and phthalocyanines are promising candidates for single-molecule electronics. Among the many characterization tools, scanning tunneling microscopy (STM) represents a very powerful one to gain insight into the electronic properties at the molecular level, by correlating the charge transport behaviours of π-conjugated molecules with ultrahigh resolution imaging. In view of the sophistication of molecular self-assembly in the presence of a solution phase, in this frontier, we focus on STM studies on porphyrins and phthalocyanines at the liquid/solid interface, placing emphasis on the electronic and magnetic properties, as well as the switching behaviour of surface-confined or surface-anchored molecules. Furthermore, we have also addressed the topics of potential that can be exploited in this area.