Novel hollow molecularly imprinted polymer (HMIPs) microspheres were synthesized via two-stage dispersion polymerization and swelling seed polymerization technique with nicotinamide (NAM) as the template molecule. Binding experiments showed that the HMIPs possessed excellent binding properties toward N-nitroamines, including fast mass transfer rate, and efficient adsorption performance with the adsorption capacity reaching up to 1.7mg/g, which was 3 times higher than that of hollow non-imprinted polymers (HNIPs). The fast binding kinetics for one N-nitrosamine (4-(methylnitrosamino)-1-(3-pyridine)-1-butanone, NNK) was attributed to the hollow porous structure with the imprinted cavities on both external and internal surface of the HMIPs.