The specific crystallographic features of M1/4TiS2 (M = Ni, Fe) lead us to carry out UHV-Scanning Tunneling Microscopy studies, in order to bring the different atoms chemical environment of the structure and the host-guest interactions to light. We imaged the top sulfur planes (001) for both compounds and proposed an explanation to the two well differentiated contrast observed and a surface structural arrangement. S2p XPS core spectra were recorded to highlight the different chemical surrounding for chalcogen atoms and their differentiation depending of the compound considered (Ni or Fe1/4TiS2).