Nanoparticles are often added to coatings in order to improve their mechanical properties. However, nanoparticles can also influence the cross-linking reaction of polymers and overall curing kinetics, and from this follows that properties of interest are further impacted. In research studies on alkyd-based coatings, only the physical drying stage during the first 24 h has been studied in this respect until now. In this study, it was shown with the use of Raman spectroscopy that colloidal nano-silica can change the rate of alkyd autoxidation and how this effect is reflected on the tensile properties of the coating. One of the consequences of the influence of nano-silica on curing kinetics is that, contrary to implicit assumptions of common testing methods, the real effect of nanoparticles on mechanical properties can emerge much later in the coating lifetime.