In this study, a new extraction approach for liquid samples--stir cake sorptive extraction using monoliths as extractive medium was developed. The preparation procedure of stir cake is very simple. First, monolithic cake is synthesized according to the in situ polymerization of monolith; then, the cake is inserted in an original unit (holder), which is constructed from a syringe cartridge and allows the magnetic stirring of the cake during the extraction process. The effects of dimension of monolithic cake and unit design on the extraction performance were optimized in detail. To demonstrate the usability of this new extraction approach, poly(vinylimidazole-divinylbenzene) was prepared and acted as the extractive cake. The analysis of steroid hormones in milk samples by the combination of stir cake with high-performance liquid chromatography with diode array detection, was selected as a paradigm for the practical evaluation of stir cake sorptive extraction. Under the optimized extraction conditions, low detection limits (S/N=3) and quantification limits (S/N=10) of the proposed method for the target analytes were achieved within the range between 0.33-0.69 and 1.08-2.28 μg/L, respectively. The method also showed good linearity, repeatability, high feasibility and acceptable recoveries. Because the monolithic cake does not contact with the vessel wall during stirring, there is no friction loss of extractive medium and the stir cake can be used for more than 1000 h.