Excessive fluoride anions in drinking water are toxic to the health of human beings. In this article, an effective fluoride removal adsorbent on the basis of amino-functionalized porous polydivinylbenzene (PDVB) was prepared through low cost processes, which included solvothermal preparation of porous PDVB and subsequent surface amino-functionalization. The obtained amino-functionalized porous PDVB (A-PDVB) has high surface area of 443 m2 g−1 and high adsorption capacity towards fluoride anion up to 105.9 mg g−1. Considering adsorbents surface area, the adsorption capacity per unit surface area of A-PDVB is 0.24 mg m−2 which is more than 4 times of porous PDVB (0.058 mg m−2). The enhanced adsorption performance of A-PDVB was due to amino groups electrostatic interaction coupled with hydrogen bond binding with fluoride anions. In addition, the amino-functionalized porous PDVB could be regenerated in high efficiency under alkaline conditions. This work not only exhibits the possibility of A-PDVB for application as an environment-friendly adsorbent for fluoride removal but also gives an insight into understanding mechanism of the fluoride anions adsorption onto amino-functionalized porous PDVB.