This study aimed at elucidating some characteristics of the shock wave overpressure generated by a non-traditional layered charge comprising an inner high-energy explosive and an outer polymer matrix composite. Two models for predicting the peak overpressure (Δpm) of the charge were established, namely, a model based on the initial parameters of the blast wave, and a model considering the weakening of the explosion energy through the introduction of polymer matrix cladding. The overpressure of a typical layered charge was experimentally measured for model validation. It was found that the difference between the Δpm predicted by the two models and the experimental data is less than 15.12% and 14.17%, respectively. The model that was established based on the conservation of energy law, is in best agreement with the experimental data under different cladding/charge mass ratios (αm). The model that was based on the initial parameters of the blast wave obtained a low predicted value when αm was 0.4–0.8, which is attributed to the non-uniformity of the gas-solid mixture during the explosive dispersion stage.