Nanostructured TiO2 thin films were fabricated via a facile, economical, and energy-efficient microwave-assisted dip-coating (MWDC) technique. Further, the resulting TiO2 films were characterized by means of X-ray diffraction, high-resolution transmission electron microscopy, selected-area electron diffraction, Fourier transform Raman spectroscopy, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy techniques for their phase structure, morphology, and optical and surface properties. TiO2-mediated photoelectrocatalytic degradation of the antibiotic cefotaxime (CFX) in an aqueous solution was studied by varying the pH under UV illumination. The degradation intermediates and possible reaction degradation path of CFX were analyzed by electrospray ionization time-of-flight mass spectrometry (MS). The MS spectra revealed that degradation of CFX occurs through beta-lactum corresponding to the cleavage of the cephem nucleus. Moreover, the antibacterial activity of CFX prior to and after photoelectrocatalytic degradation was carried out to analyze the toxicity against Staphylococcus aureus and salmonella typhi bacteria. Interestingly, it was observed that the antibiotic activity was drastically inhibited after photoelectrocatalytic degradation of the CFX solution. The photoelectrocatalytic stability of a nanostructured TiO2 electrode was evaluated by recycling the degradation experiments. It was observed that there was no significant decrease in the catalytic activity, indicating potential applications of the TiO2 electrode prepared by the MWDC method.