A method for the determination of ten photoinitiators (PIs), benzophenone, ethyl 4-dimethylaminobenzoate, 1-hydroxycyclohexyl-phenylketone, 4-methylbenzophenone, 2-ethylhexyl-4-dimethylaminobenzoate, 4-chlorobenzophenone, 2-chlorothioxanthone, 2-isopropylthio-xanthone, 2,2-dimethoxy-2-phenylacetophenone, methyl 2-benzoylbenzoate, in 13 kinds of fruit juice and 3 kinds of tea beverage has been established, using solid-phase micro-extraction (SPME) combined with chromatography/mass spectrometry (GC/MS). At first, the major factors of SPME, extraction time and temperature, were studied through orthogonal experiment. Then the optimal operation conditions were obtained via the refinement of various factors. After the sample was extracted by SPME, it was desorbed for target analytes in sampling inlet for 3 min, and separated on an HP-5MS column, then detected by MS in selected ion monitoring mode, and quantified through calibration curve. The working curves were obtained using sample matrix in order to eliminate the matrix interference. The linear range was from 0.3 microg/L to 60 microg/L and the detection limit range was from 3 ng/L to 16 ng/L. The samples were determined five times with four different spiked levels individually and the relative standard deviations of all the samples were less than 14.5%. This determination method was applied in 16 kinds of packed beverages with different brands and different species. Benzophenone had been detected from all the samples. 4-Methylbenzophenone, 2-ethylhexyl-4-dimethylaminobenzoate, 2-isopropylthioxanthone, 1-hydroxycyclohexyl-phenylketone and 2-chlorothioxanthone had been detected from a portion of samples. Simultaneous determination was achieved for the ten PIs. These results provide a reference to determine the PIs migrated from packing materials in beverage. This method is simple, high sensitive and non-polluting.