This article reports a study on structural characterization, thermal stability, and prediction of the thermal degradation mechanisms of urea–formaldehyde cellulose (UFC) composites filled with tin particles by condensed phase kinetic approaches. Structural characterization of UFC/Sn composites performed by scanning electron microscopy, X‐ray diffraction, and Fourier‐transform infrared analyses demonstrates that the composites are fairly homogenous, and the interactions between UFC and tin in the composites are physical in nature. Measurements of inherent thermal stabilities, apparent reaction profiles, and thermal degradation kinetics of UFC and UFC/Sn composites have been carried out on the thermoanalytical data of materials. The integral procedure decompositions temperature elucidates the increasing thermal stabilities trend of UFC/Sn composites with the increase in tin contents in UFC matrix. Reaction profiles of UFC and UFC/Sn composites suggest considerably complex thermal degradation pathways of the materials which comprise various competitive/consecutive reactions. Substantial variations in the activation energies of matrix and composites with the advancement of reaction by generalized integral isoconversional method verify their multistep reaction mechanisms. Advanced reaction model determination methodology with the help of a novel kinetic function F(α, T) reveals that the multistep thermal degradation of UFC goes to completion by overall following intricate nucleation/growth mechanisms. A detailed account of the mechanistic information related to thermal degradation of UFC and UFC/Sn composites is also given and discussed in this study. POLYM. COMPOS., 39:4341–4354, 2018. © 2017 Society of Plastics Engineers