Polar organic compounds (POCs) are one of the main categories of pollutants in wastewater, and their effective removal is highly desirable. In this work a novel hyper-cross-linked polyphosphamide resin (HPR) with flexible structure and functional groups for POCs adsorption was synthesized and characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Phenol, a typical POC, was used to test its adsorption amount. The experimental results showed that the polrner exhibited an excellent phenol adsorptive capacity of 516 mg g(-1) in phenol aqueous solution, though its surface area was 14.5 m(2) g(-1) only. The influences of pH, contact time, and the zero point charges of adsorption were investigated. This research provides a new and effective approach to separate and recover phenols, especially at a high concentration, from wastewater.