Pulsed laser ablation (PLA) under active liquid confinement, also known as chemical etching enhanced pulsed laser ablation (CE-PLA), has emerged as a novel laser processing methodology, which breaks the current major limitation in underwater PLA caused by the breakdown plasma and effectively improves the efficiencies of underwater PLA-based processes, such as laser-assisted nano-/micro-machining and laser shock processing. Despite of experimental efforts, little attention has been paid on CE-PLA process modeling. In this study, an extended two-temperature model is proposed to predict the temporal/spatial evolution of the electron-lattice temperature and the ablation rate in the CE-PLA process. The model is developed with considerations on the temperature-dependent electronic thermal properties and optical properties of the target material. The ablation rate is formulated by incorporating the mutual promotion between ablation and etching processes. The simulation results are validated by the experimental data of CE-PLA of zinc under the liquid confinement of hydrogen peroxide.