Porous organic polymers (POPs) based on calix[4]arene with a hydrophobic π-rich cavity and host-guest recognition properties exhibit a wide application range of molecular extraction and separation. However, it is still a challenge to improve the extraction and separation selectivity by exploring and seeking appropriate building blocks for the functionalization and pore size adjustment of calix[4]arene. Herein, an azophenyl calix[4]arene porous organic polymer (AC-POP) was proposed. By introducing an electron-rich cavity and adjusting the pore sizes of calix[4]arene, the AC-POP showed high selectivity extraction performance in triphenylmethane (TPM) dyes. The extraction mechanism was explored by adsorption thermodynamics study, density functional theory (DFT) calculation, and reduced density gradient (RDG) and electrostatic potential (ESP) analyses, which suggested that the selectivity adsorption of TPM dyes based on AC-POP was mainly the result of entropy driven by the hydrophobic effect. In addition, the noncovalent interactions including π-π stacking, van der Waals force, and electrostatic interaction were also important factors affecting the adsorption capacity of TPM dyes. Under optimal extraction conditions, the AC-POP possessed a maximum extraction amount of 95.3 mg·g^-1 for Rhodamine B (RB), high enrichment factor of about 100, and excellent reusability more than 10 times. Then, an analytical method of TPM dyes with AC-POP as a solid-phase extractant combined with high-performance liquid chromatography-ultraviolet (HPLC-UV) was established, which displayed excellent sensitivity with the limits of detection (LODs) and limits of quantitation (LOQs) in the ranges of 0.004-0.35 and 0.016-1.16, respectively. The mean recoveries for TPM dyes ranged from 85.0 to 109.4% with an RSD of 0.48-9.45%. The proposed method was successfully applied to the analysis of the five TPM dyes in seafood matrix samples.