Carboxylic acid terminated (–COOH) monolayers (ML) have been covalently anchored on the surface (S) of crystalline silicon (Si) and silicon nitride (Si₃N₄) by using wet-chemistry methods. Their concentration has been determined adopting a stepwise procedure with a fluorescent probe in solution. First, 7-amino-4-methylcoumarin (H₂N–C₁₀H₇O₂, AMC) is covalently bonded to the monolayer on the surface through an amidation reaction forming an amide-terminated surface monolayer, S–(CH₂)_n–CO–NH–C₁₀H₇O₂, then the surface is intensely washed in order to remove any physisorbed species, finally AMC is detached from the surface via hydrolysis of the –CO–NH– bond and quantified by a fluorescence analysis in water solution. The yields of both the amidation and hydrolysis reactions have been evaluated. By this method, submonolayers ≤0.1 ± 0.03 ML can be determined. It has been possible to evaluate the different extent of surface functionalization changing the substrate between Si and Si₃N₄ and for Si changing the monolayer formation reaction: heat- (Δ) or light- (hν) promoted or via cathodic electrografting (CEG). It came out that submonolayers are formed in any case, Si₃N₄ is functionalized to a larger extent than Si on heating (0.52 vs. 0.15 ML) and Si is best functionalized via cathodic electrografting: Δ, 0.15; hν 0.20; CEG, 0.44 ML. Surface topography of some monolayers on Si and Si₃N₄ substrates was investigated by Atomic Force Microscopy (AFM). On clean Si, AFM showed topographical variations of 0.3–0.4 nm while for the clean Si₃N₄ the corrugation was around 3–4 nm. After functionalization the two surfaces were uniformly covered and the corrugation increased in both samples with a corrugation in topography of 1–2 nm for Si and 5–6 nm for Si₃N₄.