Functional polymer brushes have a tremendous interest for surface engineering, thanks to stimuli-responsive behavior, allowing applications in the field of switchable wettability/adhesion, controlled release and sensor development. However, surface-attached polymer brushes are very difficult to characterize with standard techniques like GPC and NMR due to the very small amount of polymer grafted (~0.01 mg cm-2). Thus, more sophisticated (and expensive) techniques, i.e. XPS, are needed in order to achieve a satisfactory knowledge of the sample under study. In this work, poly(dimethylaminoethyl methacrylate) (PDMAEMA) homopolymer brushes and poly(hydroxyethyl methacrylate-r-aminoethyl methacrylate) (PHEMA-r-PAMA) random copolymer brushes (employing two different compositions of the polymerization feed) were synthesized by the “grafting-from” approach, performing surface-initiated atom transfer radical polymerization (SI-ATRP) on surfaces functionalized with an alkoxysilane-type initiator. PDMAEMA was chosen for its pH-responsive properties and its affinity for metal nanoparticles, PHEMA-r-PAMA for the post-functionalization opportunities allowed by hydroxyl and primary amine groups (e.g. coupling of fluorophores). Every step of the grafting procedure, from surface pretreatment to functionalization with initiator and eventually the grafted brushes, was studied using electrochemical techniques, in particular cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). In this way, the homogeneity and density of the initiator layer and of the resulting brushes, their composition and thickness and also the efficiency of nanoparticle incorporation and post-functionalization reactions could be easily investigated.