The complex sample matrix and low environmental concentration make it challenging to effectively determine the polar glucocorticoids. In particular, a green, economical, and environmentally friendly method is urgently needed, since a large amount of extraction solvents, samples, and extraction materials have been commonly used to improve the sensitivity of the reported methods. In this study, a green and robust phenol and bismuth-based MOF of SU101 was mildly synthesized and fabricated as a brand new solid-phase microextraction (SPME) fiber. Only tiny amounts of SU101 and desorption solvents were employed to realize the high-efficiency enrichments of glucocorticoids from water samples. The detection performance of proposed SU101 fiber towards glucocorticoids was much superior to the single-component and multi-component commercial fibers. It indicated that SU101 fiber could be an excellent candidate for the enrichments of polar pharmaceuticals. After it was coupled with the instrument of high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS), the linear range of 5–10000 ng L−1 with detection limits low to 0.070–1.5 ng L−1 and satisfactory recoveries were achieved by the developed method. Benefiting from the environmental friendliness of SU101 and the less-solvent consumption of SPME technique, this work presented a green and economical strategy for determinations of trace glucocorticoids.