The washed process is one of the traditional post-harvest processes of coffee beans, which include selective harvesting, flotation, pulping, submerged fermentation underwater, washing, and drying operations. During the washed processing, fermentation underwater can remove coffee mucilage and change metabolites by microorganisms. Therefore, coffee fermentation is a key factor influencing coffee’s flavor. To compare the influence of fermentation duration in an open environment of Coffea arabica in 48 h during the washed processing on the coffee’s flavor, the sensory characteristics of the coffee at different fermentation durations were evaluated using the Specialty Coffee Association of America (SCAA) cupping protocol. Moreover, ultra performance liquid chromatography–triple quadrupole mass spectrometry (UHPLC–MS/MS) and gas chromatography–mass spectrometry (GC–MS) were combined to analyze and compare the chemical compounds of coffee samples from fermentation durations of 24 h (W24) and 36 h (W36) during the washed processing method. The results showed that W36 had the highest total cupping score with 77.25 in all different fermentation duration coffee samples, and 2567 non-volatile compounds (nVCs) and 176 volatile compounds (VCs) were detected in W36 and W24 during the washed processing method. Furthermore, 43 differentially changed non-volatile compounds (DCnVCs) and 22 differentially changed volatile compounds (DCVCs) were detected in W36 vs. W24. Therefore, suitable fermentation duration in an open environment is beneficial to coffee flavor, judging by chemical compound changes. For the washed primary processing of C. arabica from Yunnan, China, 36 h fermentation was the suitable fermentation duration in an open environment, which presented potential value as the reference for washed coffee processing in the food industry.