A molecularly imprinted polymer (MIP) for highly selective solid-phase extraction (SPE) of bisphenol A (BPA) was prepared using phenolphthalein (PP) as the novel dummy template by bulk polymerization. A particle diameter distribution of 40–60 μm, a specific surface area of 359.8 m²·g⁻¹, and a total pore volume of 0.730 cm³·g⁻¹ for the prepared PP-imprinted polymer (PPMIP) were obtained. Good selectivity and specific adsorption capacity for BPA of the prepared PPMIP were also demonstrated by the chromatographic evaluation and sorption experiments. The PPMIP as a SPE sorbent was evaluated for the selective extraction and clean-up of BPA from complex biological, environmental, and food samples. Meanwhile, an accurate and sensitive analytical method based on the PPMIP-SPE purification procedure coupled with high performance liquid chromatography-diode array detector (HPLC-DAD) detection has been successfully developed for the rapid determination of BPA from these samples, with detection limits of 1.3 ng·mL⁻¹ for bovine serum and milk, 2.6 ng·mL⁻¹ for human urine and edible oil, 5.2 ng·mL⁻¹ for soybean sauce, and 1.3 ng·g⁻¹ for sediment. The BPA recoveries at two different spiking levels were in the range of 82.1–106.9%, with relative standard deviation (RSD) values below 7.7%.