This work aims to investigate the effect of process temperature and catalyst content by pyrolysis and thermal catalytic cracking of (organic matter + paper) fraction from municipal household solid waste (MHSW) on the yields of reaction products (bio-oil, bio-char, H2O, and gas), acid value and chemical composition of bio-oils, and characterization of bio-chars, in laboratory scale. The collecting sectors of MHSW in the municipality of Belém-Pará-Brazil were chosen based on geographic and socio-economic database. The MHSW collected and transported to the segregation area. The gravimetric analysis of MHSW carried out and the fractions (Paper, Cardboard, Tetra Pack, Hard Plastic, Soft Plastic, Metal, Glass, Organic Matter, and Inert) separated. The selected organic matter and paper submitted to pre-treatment of crushing, drying, and sieving. The experiments carried out at 400, 450, and 475 °C and 1.0 atmosphere, and at 475 °C and 1.0 atmosphere, using 5.0, 10.0, and 15.0% (wt.) Ca(OH)2, in batch mode. The bio-oil characterized for acid value. The chemical functions present in bio-oil identified by FT-IR and the composition by GC-MS. The bio-char characterized by SEM, FT-IR and XRD. The variance in mass (wt.%) for organic fraction of municipal household solid waste, between 56.21 and 67.45% (wt.), lies with the interval of 56% (wt.) and 64% (wt.) of OFMHSW for middle and low income countries. The pyrolysis of MHSW fraction (organic matter + paper) show bio-oil yields between 2.63 and 9.41% (wt.), aqueous phase yields between 28.58 and 35.08% (wt.), solid phase yields between 35.29 and 45.75% (wt.), and gas yields between 16.54 and 26.72% (wt.). The bio-oil yield increases with pyrolysis temperature. For the catalytic cracking, the bio-oil and gas yields increase slightly with CaO content, while that of bio-char decreases, and the H2O phase remains constant. The GC-MS of liquid reaction products identified the presence of hydrocarbons (alkanes, alkenes, alkynes, cycloalkanes, and aromatics) and oxygenates (carboxylic acids, ketones, esters, alcohols, phenols, and aldehydes), as well as compounds containing nitrogen, including amides and amines. The acidity of bio-oil decreases with increasing process temperature and with aid Ca(OH)2 as catalyst. The concentration of hydrocarbons in bio-oil increases with increasing Ca(OH)2-to-MHSW fraction ratio due to the catalytic deoxygenation of fatty acids molecules, by means of de-carboxylation/de-carbonylation, producing aliphatic and aromatic hydrocarbons.