The controlled release of active agents from a matrix has become increasingly important for oral, transdermal or implantable therapeutic systems, due to the advantages of safety, efficacy and patient convenience. Controlled-release hybrid (organic-inorganic) sol-gel coating synthesis has been performed to create a sol with an active molecule included (procaine). Synthesis procedures included acid-catalysed hydrolysis, sol preparation, the addition of a procaine solution to the sol, and the subsequent gelation and drying. The alkoxide precursors used were triethoxyvinylsilane and tetraethyl-orthosilicate (TEOS) in molar ratios of 1:0, 9:1, 8:2 and 7:3. After the determination of the optimal synthesis parameters, the material was physicochemically characterised by silicon-29 nuclear magnetic resonance (Si-29-NMR) and Fourier transform infrared spectroscopy, contact angle analysis and electrochemical impedance spectroscopy tests. Finally, the materials were assayed in vitro for their ability to degrade by hydrolysis and to release procaine in a controlled manner. The sustained release of procaine over a 3-day period was demonstrated. A close correlation between release and degradation rates suggests that film degradation is the main mechanism underlying the control of release. Electrochemical analysis reveals the formation of pores and water uptake during the degradation. The quantity of TEOS is one of the principal parameters used to determine the kinetics of degradation and procaine release.