A model of smolder for cellulose-containing materials is presented. The components of a system are determined to include the products of cellulosic defragmentation, oxygen, water, alkali and transition metals, radical initiators and inhibitors. Smolder and combustion of cellulosic fabrics were investigated by means of DSC/TG/MS, TPR/GC, and IR thermographic systems in inert and O2 -containing atmosphere. Mass diffusion, heat transfer, and reaction kinetic parameters of cellulosic smolder were experimentally determined. Smolder of an upholstery fabric was found to be controlled by oxygen diffusion. A chemical model of oxygen and water-driven alkali-assisted decomposition of cellulose was suggested. Some peculiarities in a smolder behavior of dyed fabrics were investigated and explained by a competitive action of alkali metal compounds and pigment compounds. The mechanism of production of carbon oxides during smolder process has been studied.