As an emerging porous material, hydrogen-bonded organic framework materials (HOFs) still pose application challenges. In this work, the designed type “I + II” heterojunction extracted hot electrons from HOFs using quantum dots (QDs) and polypyrrole (Ppy), improving the stability and photoelectrochemical performance of materials. In addition to serving as a potential well, electropolymerized Ppy was used as a recognition element for bisphenol A (BPA), and a novel self-powered molecularly imprinted photoelectrochemical (MIP–PEC) sensor was designed. The sensing platform showed a linear relationship from 1 × 10−10 to 1 × 10−7 mol∙L−1 and from 1 × 10−7 to 1 mol∙L−1 with an acceptable detection limit of 4.2 × 10−11 mol∙L−1. This is the first application of HOFs in constructing MIP–PEC sensors and a new attempt to improve the stability of HOFs for the application of porous crystal materials in the sensing field.