By taking salted chili as materials, the fermentation process in making desalted chili were optimized through orthogonal experiment, and the change of volatile flavor components before and after fermentation were determined by headspace solid phase microextraction gas chromatography and mass spectrometry (HS–SPME–GC–MS). The results indicated that NaCl, total sugar, total acid, reducing sugar and amino acid nitrogen content in desalted chili reduced significantly after desalination (P<0.05). The appropriate fermentation process of desalted chili was 6% Lactobacillus plantarum, 4% sugar, and fermentation for 5 days. The relative content of esters and aldehydes of inoculation fermentation desalted chili increased 24% and 448% respectively than desalted chili, while alcohols and olefins decreased 18% and 31% respectively. Inoculation fermentation was helpful to improve the flavor of esters and aldehydes in chili.