The electrochemical reduction of 1,10-phenanthroline in aqueous acidic electrolyte at a glassy carbon electrode led to the covalent modification of the electrode. Thereafter, the deposited film can be switched to an electroactive form by electrochemical oxidation. An electroactive film can be also generated by alternate reductive and oxidative voltammetric cycling in a 1,10-phenanthroline/aqueous sulfuric acid solution. First, the electrochemical procedure for the formation of a film is presented. Second, the morphology and chemical structure of 1,10-phenanthroline coatings were investigated by atomic force microscopy, time-of-flight secondary ion mass spectrometry, X-ray photoelectron spectroscopy, and electrochemical techniques. The ultrathin (<15 nm) electrodeposited films consist of oligomeric species. The coatings deposited in alternate and/or continuous reductive and oxidative steps contain oxygen atoms incorporated into the oligomer backbone. The preliminary results point out the formation of a dione derivative that is responsible for the electroactivity of the grafted layer.