An analytical model for volatile organic compounds (VOCs) transport through a composite liner consisting of a geomembrane (GM), a geosynthetic clay liner (GCL), and a soil liner (SL) was developed for the assessment of the performance of this triple liner system. Both advection through the defects of GM and diffusion in the intact GM were considered in the model, and dimensionless analytical solution was obtained. The soil concentration profiles obtained by the proposed analytical solution have a good agreement with those obtained by the finite-layer-based software POLLUTE v7. The effects of leachate head, length of the connected wrinkles, and the interface transmissivity of GM/GCL on the breakthrough curves of the liner system were then investigated. Results show that the 30-year base flux of the liner system for the case with leachate head = 10 m and length of the connected wrinkles = 1,000 m can be over 60 times greater than that of the pure diffusion case. The length of the connected wrinkles of the GM has greater influence on the base flux of the liner system than on the base concentration. The interface transmissivity has negligible effect on the solute breakthrough curves of the liner system for relatively low values of the length of the connected wrinkles (e.g., <100 m). The groundwater protection level achieved by GM/CCL is more effective than that by GM/GCL/SL in the earlier times. However, the steady state base flux for GM/GCL/SL can be seven to eight times lower than that for GM/CCL. The analytical solution can also be used for experimental data fitting, verification of complicated numerical models, and preliminary design of composite liners.