The heating value describes the energy content of any fuel. In this study, this parameter was evaluated for different abundant materials in Morocco (two types of biochar, plastic, synthetic rubber, and cardboard as municipal solid waste (MSW), and various types of biomass). Before the evaluation of their higher heating value (HHV) by a calorimeter device, the thermal behavior of these materials was investigated using thermogravimetric (TGA) and Differential scanning calorimetry (DSC) analyses. The focus of this work is to evaluate the calorific value of each material alone in a first time, then to compare the experimental and theoretical HHV of their mixtures in a second time. The heating value of lignocellulosic materials was between 12.16 and 20.53 MJ/kg, 27.39 for biochar 1, 32.60 MJ/kg for biochar 2, 37.81 and 38.00 MJ/kg for plastic and synthetic rubber respectively and 13.81 MJ/kg for cardboard. A significant difference was observed between the measured and estimated HHVs of mixtures. Experimentally, results for a large variety of mixture between biomass/biochar and biomass/MSW have shown that the interaction between biomass and other compounds expressed a synergy of 2.37% for biochar 1 and 6.11% for biochar 2, 1.09% for cardboard, 5.09% for plastic and 5.01% for synthetic rubber.