In this study, a novel aluminum phosphate (AlPO4) heat‐resistant layer reinforced with aluminum silicate fiber (ASF) was successfully compounded on a poly(ether sulfone) (PES) matrix via the preparation process of high‐temperature heat treatment and vacuum hot‐pressing sintering technique. The influence of the ASF content on the morphology, thermal, mechanical, and dielectric properties of the as‐fabricated aluminum silicate fiber reinforced aluminum phosphate–poly(ether sulfone) (ASF/AlPO4–PES) layered composite was investigated. The results reveal that the incorporation of aluminum silicate fiber/aluminum phosphate (ASF/AlPO4) heat‐resistant layer can significantly improve the thermal stability and mechanical performances of the PES matrix composites. Compared with the pristine PES, the ASF/AlPO4–PES layered composite containing 8.0 wt % ASF exhibited better high‐temperature resistance properties (300 °C) and a lower thermal conductivity (0.16 W m−1 K−1). Furthermore, the dielectric constant and dielectric loss tangent of this PES matrix composite decreased to 2.16 and 0.007, respectively. Meanwhile, the frequency stability of the dielectric properties for the ASF/AlPO4–PES layered composites was remarkably enhanced with increasing ASF addition at frequencies ranging from 102 Hz to 5 MHz. This was attributed to the existence of microscopic pores within the ASF/AlPO4 layer and the strong interfacial bonding between the ASF/AlPO4 layer and the PES matrix. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45542.