Solid-phase microextraction (SPME) has gained widespread acceptance in sample pretreatment due to its solvent-free and easy-to-operate properties. SPME fibers are considered as a key part of SPME technique, since it primarily determines the extraction performance of the method including sensitivity, selectivity, and reproducibility. Generally speaking, target analyte with different chemical property requires fiber coating that has the best affinity towards it. Due to the lack of varieties of commercial fibers available currently, considerable efforts have been recently made to develop tailor-made fibers to fulfill increasing demands of different analysis. This paper concisely classify some SPME fiber preparation approaches such as sol-gel technology, physical deposition, molecularly imprinted technique, and their respective application in food safety analysis.