Low temperature enrichment coupled with GC-MS was established for the identification of fruit compounds in Nanfeng Oranges via optimization of solvent selection，frozen temperature and frozen time of sample pretreatment.The optimized conditions were as the follows:extraction solvent:n-hexane， frozen temperature:-40 ℃，frozen time:1 h.Under the optimal conditions， 64 main compounds，including esters，terpenes，alcohols and alkanes compounds were identified with the help of retention indices.Compared with the results of traditional ambient liquid-liquid extraction and reported，the established method could present a selective enrichment for substances with polarity,poor thermal stabilitiy and difficult volatility.