Amorphous calcium phosphate (ACP) microspheres with a porous and hollow structure have been prepared using an aqueous solution containing CaCl2 as a calcium source, adenosine triphosphate disodium salt (Na(2)ATP) as a phosphorus source in the presence of a block copolymer methoxyl poly(ethylene glycol)-block-poly(D,L-lactide) (mPEG-PLA) by the microwave-assisted hydrothermal method. The effects of microwave hydrothermal temperature and the concentrations of CaCl2 and Na(2)ATP on the crystal phase and morphology of the product are investigated. The as-prepared ACP porous hollow microspheres have a relatively high specific surface area of 232.9 m(2) g(-1) and an average pore size of 9.9 nm. A typical anticancer drug, docetaxel, is used to evaluate the drug loading ability and drug release behavior of ACP porous hollow microspheres in phosphate buffered saline (PBS) with different pH values of 4.5 and 7.4. The experiments reveal that the ACP porous hollow microspheres have a high drug loading capacity and favorable pH-responsive drug release property, and the ACP porous hollow microsphere drug delivery system shows a high ability to damage tumor cells. It is expected that the as-prepared ACP porous hollow microspheres are promising for the applications in various biomedical fields such as drug delivery. (C) 2014 Elsevier Inc. All rights reserved.