Understanding and sensing microbial biofilm formation onto surfaces remains highly challenging for preventing corrosion and biofouling processes. For that purpose, we have thoroughly investigated biofilm formation onto glassy carbon electrode surfaces by using electrochemical technics. Pseudomonas aeruginosa was studied because of its remarkable ability to form biofilms in many environments. The modification of the electrode-solution interface during biofilm growth was monitored by in-situ measurement of the open-circuit potential and correlated with results obtained by electrochemical impedance spectroscopy, cyclic voltammetry, scanning electron microscopy and bioassays. The sensing of the biofilm formation hence suggests a multi-steps mechanism, which may include pre-formation of an insulating layer onto the surface prior to the bacteria adhesion and biofilm formation.