The remarkable properties of polysulfone (PSF) membranes have contributed to their use in many ultrafiltration applications. Meanwhile, this huge usage of PSF films and its short service life have generated a huge amount of waste PSF films that need to be managed carefully. Within this framework, this is the first research specifically developed to valorize the end-of-life of PSF membranes and convert them into high-value chemical and energy products using pyrolysis treatment. The treatment was performed using a thermogravimetric analyzer (TGA), while the structure and abundance of the phenol and benzoic acid compounds in the generated vapor were determined using Fourier-transform infrared (FTIR) spectroscopy and Gas chromatography-mass spectrometry (GC-MS). Thermogravimetric recorded data at different conditions (5–30°C/min) was subjected to linear and nonlinear models including KAS, FWO, Friedman, Vyazovkin, and Cai to assess the pyrolytic kinetic behavior of PSF films. The films showed higher content of volatile matter (57%), lower NOx emissions (0.321%), and a little bit more SOX emission (6.909%). The GC-MS showed that the pyrolytic gaseous products are rich in phenol (24.3%) and benzoic acid (52.4%) compounds and the highest abundance was achieved at 30°C/min. Whereas activation energies were estimated in the range of 193–240 kJ/mol based on linear kinetic criteria versus 161–163 kJ/mol in the case of nonlinear models, where R2 values (>0.91) indicated perfection. Also, distributed activation energy and independent parallel reaction kinetic models showed a good fit with the TGA-DTG experimental data with the minimum deviation. The study confirmed the potential of pyrolysis treatment in converting wasted PSF films into a new source for the recovery of phenolic and benzoic acid.