Fabrication of hydrophobic composite resin for enhancing oil-water or organic solvents-water separation applications has become increasingly attractive due to increasing industrial/domestic oily waste water and frequent oil accidents. In this work, firstly, carbonized pollen grain (PG) containing biological structure was prepared with rapeseed flower by the removing impurities, dehydration and calcinations. The morphologies of the synthesized PG show that they are ellipsoidal and hollow particles with length of ca. 30 mu m, and pollen shell has a uniform network structure with an average pore size of 1.5 mu m. Cross-sectional image of PG shows a palisade-like shell with the thickness of about 1 gm and vast pore canals. Outstanding BET surface area (379.98 m(2) g(-1)) is achieved. Secondly, hydrophobic pollen grain (HPG) was prepared with PG by the surface activation and vinyltriethoxysilane (A151) modification under microwave-treated technique. The static contact angle for deionized water on HPG is 132, indicating its excellent hydrophobic nature. Furthermore, a series of 3D hydrophobic composite resins (HCR) network decorated with different HPG content were prepared by the method of suspension polymerization under microwave conditions and benzoperoxide as initiator. Enhancing absorption capacities of 16.8 and 58.8 g g-1 to oils and organic solvents, respectively, are achieved. Pseudo-second-order and intra-particle diffusion kinetic models were employed for the corresponding organic solvents and oil absorption. This work represents a low cost, clean, and efficient route to prepare hydrophobic composite resin for absorption of oils and organic solvents with high performance, including absorption capacity, excellent selective separation performance on immiscible oilwater mixtures, good structural stability and reusability. (C) 2017 Elsevier B.V. All rights reserved.