Experimental and theoretical studies have been conducted on the thermal destruction behavior of 100% cellulose and mixture of 90% cellulose-10% polyethylene (C13H8O7) in a laboratory scale facility. A series of pyrolysis and oxidative pyrolysis (pyrolysis followed by air or oxygen addition) tests were performed. Temperature was varied from 600 to 1500K. Data provides the effect of temperature, air addition and chemical composition of the surrogate solid waste on the emissions of NOx, CO, CO2 and unburnt hydrocarbons (HC). Thermal destruction behavior of the surrogate waste is qualitatively observed to be enhanced with the progressive increase in temperature which also results in increased reduction of the material volume. Numerical calculations using equilibrium conditions are used to describe the experimentally observed trends for the thermal decomposition behavior of these materials. Analysis of the data reveals that composition of the waste as well as conditions under which the process of thermal destruction takes place (i.e., temperature, excess air or oxygen enrichment) and process type (combustion or pyrolysis) have significant influence on the product gas composition. The results also show significant effect of air enrichment on the distribution of species during pyrolysis and oxidative pyrolysis. These results reveal that controlled thermal destruction involving pyrolysis followed by combustion provides attractive benefits of high thermal destruction efficiency and low pollutants emission. This information can assist in developing strategies for the design and operation of thermal destruction facility.