The presence of emerging contaminants in water and wastewater resources is of ongoing concern for public health and safety. Pharmaceutical compounds are designed to be biologically active and therefore may have effects on nontarget organisms in terrestrial and aquatic environments, even at trace concentrations. The presence of pharmaceutical and personal care products (PPCPs) in wastewater treatment plants is reported in various countries worldwide, mostly in the levels of nanograms to micrograms per litre. The present study investigates the thermal degradation of municipal sewage sludge containing PPCPs at various heating rates. The examined characteristics of the samples include thermal decomposition behavior, volatile release characteristics, and pyrolytic product composition. Thermal characterization of the PPCPs was conducted using differential scanning calorimetry. The gaseous products and typical functional groups of the released volatiles detected by Fourier-transform infrared spectroscopy mainly contained CO2, CO, small-chain hydrocarbons, and oxygen- and nitrogen-containing functional groups together with other species. In addition, the potential of bioenergy production was investigated as a spin-off opportunity during thermal degradation of biosolids. Study results showed that PPCP concentrations can be lowered significantly by thermal treatment of municipal biosolids. Antifungal/antibacterial agents together with opioids, in particular triclosan and tramadol, showed less resistance to thermal degradation while antibiotics could be more recalcitrant to heat treatment. The thermodynamic results provide an important reference for future reactor design and the thermochemical treatment of biosolids as well as their conversion to value-added products.