Soil-bentonite vertical cut-off wall is an emergency technique used for contaminant control in geo-environmental engineering, high-density polyethylene (HDPE) geomembrane (GM) with an extremely low-permeability coefficient is expected to enhance the contaminant barrier effect of the vertical cut-off wall. To evaluate the barrier performance of the composite barrier composed of GM and soil-bentonite mixture towards organic contaminant, while also quantitively revealing the impact of GM defects and placement, a one-dimensional transport model for organic contaminants in composite barrier is solved under semi-infinite boundary conditions. The proposed transport model is validated by numerical simulations using COMSOL Multiphysics 5.4, and the effects of GM defect rate, placement within the composite isolation wall, and contact level with soil-bentonite on contaminant transport behavior are further studied. The results show that as the average frequency of GM defects increases from 2.5 to 50 holes per hectare, the breakthrough time of organic contaminants through composite barrier decreases by almost 70%. Poor contact level between GM and soil-bentonite mixture may reduce the breakthrough time of the composite cut-off wall by 65%. Although the selection of GM placement has limited impact on the transient flux of contaminants, it does affect the total flux of contaminants over a certain period of time. The effects of permeability coefficient, effective diffusion coefficient, distribution coefficient, and hydraulic head of the composite cut-off wall can be considered by the proposed analytical solution, which would provide guidance and reference for the design and service performance evaluation of the composite cut-off wall.