Trichloroethylene (TCE), a common chlorinated hydrocarbon and volatile organic compound (VOC), poses significant risks to environmental and human health. Its volatilization and diffusion in fractured porous media are complex and difficult to characterize. The volatilization behavior of TCE at the air-soil interface of complex dual media remains poorly understood experimentally. Simulation experiments of NAPL-phase TCE leakage in dual-media systems, combined with finite difference numerical technique, were used to qualitatively assess the influences of fracture and pore structure geometry on TCE volatilization and diffusion. The diffusional fluxes of TCE volatizedfrom the aqueous phase, calculated using effective diffusion coefficients (D_e) obtained from four empiricalandsemi-empirical models, werecompared. In addition, the contribution of volatilization fluxes of TCE from the non-aqueous phase liquid (NAPL)was also analyzed. We find the volatilization flux of TCE at the air-soil interface of the complex structure P5F3 constructed with permeable blocks made of 3~5mm gravel (P5) and a 3mm-aperture vertical fracture (F3) was lower than thatof structure P3F1. Comparison the TCE diffusional flux volatilized from the aqueous phase at the air-soil interface over the upstream-source, source, and downstream-source regions, thehighest vapor flux was estimated overfracture region, followed by the downstream-source region, with the upstream-source region showing the lowest flux. TCE vapor diffusional flux from aqueous phaseoverfracture region accounts for 3% and 5% of the total fluxover entire regionwhenthe ratio of fracture width to permeable block length is 1:150 and 1:50, respectively. The interface diffusional fluxbased on D_e from the Bartelt-Hunt model is the largest, while that from the Currie model is the smallest. The amount of vapor TCE volatized from Napl-phaseis significantly greater than that fromaqueous phase, the former may account for more than 78% of total gas-phase TCE, based on the discrepancy between the gas-phase TCE concentration measured under the sealed air chamber in the lab and the value estimated numerically from the aqueous phase alone.