Synergism during the co-pyrolysis of microalgae (CC), municipal solid waste (MSW), and their blends (CC/MSW) (w/w %), 25/75 (CM-1), 50/50 (CM-2), and 75/25 (CM-3), was evaluated based on thermal decomposition pattern, evolved gases, rate and extent of thermal decomposition, and kinetic parameters. Three stages of devolatilization attributed to dehydration, devolatilization of major structural compounds of biomass and decomposition of solid residues were noticed during the co-pyrolysis of biomass samples. The main pyrolysis stages for CC, MSW, CM-1, CM-2 and CM-3 were 175–520, 151-523, 164-504,168-510, 160–501 °C, respectively. Microalgae, CC, appeared to be thermally resistant, while MSW is noticed to be thermally sensitive. The kinetics analysis was studied by deconvoluting the DTG profile into independent stages, followed by application of isoconversional methods to evaluate the activation energy and the pre-exponential factor. Furthermore, the reaction mechanism of each stage was determined by using the master plot method. The semi-quantitative method was used to evaluate the evolved gases and CO, CO2 and H2 were noticed to be the dominant gas species. The obtained thermal and kinetic data for co-pyrolysis of microalgae and MSW can serve are basis for scale-up and reactor design of pyrolysis process for similar kind of waste streams. © 2020