Bifunctional electrocatalytic films were prepared employing a layer-by-layer assembly approach. The cation, metalloporphyrin (MP), and the anion, potassium tetrachloroaurate (KAuCl4) were alternatively assembled on glass or indium-doped tin oxide (ITO) supports. The assembled AuCl4
- ions were then converted to gold nanoparticles (Aun) under the exposure to ultraviolet light. Film growth at each adsorption step was monitored by UV-Vis absorption spectroscopy and cyclic voltammetry (CV). The formation of gold nanoparticles was characterized by UV-Vis absorption spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Bifunctional electrocatalytic activity of the film was demonstrated in the oxidative detection of nitric oxide (NO) over Aun and the reductive detection of oxygen (O2) over Co(II)P in the same CV scan.