For the analysis of covalently bound organic monolayers a variety of surface-sensitive techniques has been developed, including XPS, AES, IR, contact angle measurements and X-ray reflectivity. While each of these has its own merits, none of them provide structural information. In addition, via e.g. XPS it is sometimes possible to follow A -> B reactions on a surface, but A -> x% B + y% C is already nearly impossible to properly analyze. Similar restrictions apply to the study of diluted monolayers (e.g. 10% of a bioactive compound surrounded by 90% inert surface-covering monolayer), while dilution may actually be essential for the proper biological functioning of the monolayer! Therefore novel analysis techniques are still in demand, and here we present the application of DART ambient mass spectrometry as a generic and highly powerful technique for the analysis of such monolayers. Using a variety of tailor-made, covalently attached organic monolayers on silicon nitride and other substrates we show that MS can be used to study: 1) the progress of four sequential surface-bound organic reactions, 2) surfaces with a mixture of halogens on them, 3) the progress of incomplete reactions, and 4) the stability of biofunctional groups. In the current presentation we summarize our recently published work in this area (ChemComm 2013, 922) and present new, as of yet unpublished data that outline the tremendous potential of this novel analysis technique!