The understanding of oxidized species derived from the neurotransmitter dopamine (DA) is a relevant topic for both the medical field (Parkinson's disease) as well as for the field of materials science where the formation process of polydopamine (PDA) films is an active area of research. Polymers that interact strongly with almost all surfaces but have a low electrical conductivity have been obtained by the chemical oxidation of DA. Since electrical conductivity is a desired property for several applications, deposition alternatives such as electrochemical PDA synthesis have been proposed, but the results are still insufficient. In this context, we propose a new PDA chemical-electrochemical deposition process on glassy carbon electrodes. The chemical oxidation step that converts dopamine into dopamine-o-quinone previous to the electrochemical deposition was crucial to decrease the precursor concentration to the micromolar range. The PDA-like films synthesized by this method had high adhesion and low charge-transfer resistance, which was evidenced by impedance measurements and the successful electrodeposition of a polypyrrole coating on top of a PDA-like film. In addition, we observed that anodization of GC surfaces increases sensitivity toward six electroactive couples derived from DA oxidation in the pH regimes studied. These results show the complexity of the intermediates formed during the electrochemical polymerization of PDA.