A characterization study was carried out to determine the moisture content, proximate and ultimate compositions, heating value, and thermal weight loss behavior of fourteen different municipal solid wastes (MSW). An empirical model was developed for the high heating value (HHV) estimation of MSW: HHV (MJ/kg) = 0.350 C + 1.01 H - 0.0826 O, which is expressed in terms of weight percentages on a dry basis of carbon (C), hydrogen (H) and oxygen (O). The validation results suggest that this model was effective in producing accurate outputs that were close to the experimental values. A series of experiments pyrolysing coffee cups were also performed using zeolite type catalysts. In the presence of Ga/HZSM-5 in the mixed bed reaction, the pyrolysis oil’s effective hydrogen-to-carbon molar ratio (H/Ceff) was markedly increased, from 0.49 to 1.11. Valuable phenolic compounds were observed to be the main species in the pyrolysis oil.