The monodisperse microporous carbon nanospheres (MMCNSs) were applied in solid phase microextraction for the first time. The MMCNSs-fiber was prepared by sol-gel technique and good repeatability and reproducibility were obtained, due to the excellent monodispersity of the MMCNSs. The sol-gel-MMCNSs fiber exhibited superior extraction ability for polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs), compared with the commercial polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber and the fiber prepared with its precursor, the monodisperse microporous polystyrene nanospheres (MMPNSs). Moreover, the fiber has good thermostability and strong acid/base durability. The sol-gel-MMCNSs fiber was then employed to detect PAHs and OCPs in aqueous samples by combining with gas chromatography-mass spectrometer (GC-MS). Under the optimized conditions, the detection limits of the proposed method ranged from 0.10 to 5.5 ng L(-1). Furthermore, the method was successfully utilized for the analysis of PAHs and OCPs in real samples, with satisfactory recoveries in the range of 81.0-120% for the Pearl River water samples and 72.8-118% for the coking wastewater samples.