A fully coupled thermal–hydraulic–mechanical–chemical (THMC) model was proposed to describe the migration of volatile organic contaminations (VOCs) in unsaturated landfill liners. The vertical soil stress, capillary pressure, air pressure, temperature increase, and solute concentration were selected as the primary variables. Finite deformations were described using Lagrangian coordinates. Non-isothermal moisture transport was found to be dependent on both the temperature gradient and the concentration of the VOCs. The VOCs were assumed to exist and be transported in three phases in the soil: solid, liquid, and gas. An illustrative example of an unsaturated landfill with a compacted clay liner was presented. For the case considered, the transport of gas phase VOCs was found to dominate the migration progress. Moreover, the temperature gradient can accelerate the breakthrough of VOCs in an unsaturated liner, while the mechanical consolidation slowed down the motion of the VOCs.