The synthesis of self-assembled monolayers on Si(100) substrates of a new fluorescent Zn(II) Schiff-base complex is reported. Chemisorbed species are characterized by the combination of fluorescence scanning near-field optical/atomic force microscopy (SNOM/AFM), and by fluorescence spectroscopy. Both SNOM/AFM results indicate the existence of a monolayer on the surface, while optical SNOM images highlight the contribution of the monolayer to the local fluorescence. While chemisorbed molecular monolayers exhibit a distinct fluorescence, analogous to that observed in solution, cast thin films do not show any emission. Photoluminescent properties of the monolayer can be related to its nanoscale uniform, ordered structure.