This study aimed to explore the dynamic variations in the phenolic and volatile organic compounds of sugarcane vinegar subjected to different production processes. The determination of phenolic and volatile organic compounds was performed by UPLC-MS and solid phase micro extraction (SPME) coupled with gas chromatography combined with mass spectrometry (GC–MS). The complete fermentation process of sugarcane lasted nine days, and production of vinegar of up to 3.04% (w/v), total acids, and 4.1° alcoholicity was accomplished. Various phenolic compounds of sugarcane juice (non-sterilized) and those of alcoholic and acetic acid fermentation were obtained after nine days of fermentation. These were benzoic acid (2.024, 1.002, and 1.027 mg L–1), ferulic acid (0.060, 0.205, and 1.124 mg L–1), quinic acid (0.019, 0.074, and 0.031 mg L–1), chlorogenic acid (0.349, 1.635, and 1.217 mg L–1), apigenin (0.002, 0.099, and 0.004 mg L–1), kaempferol (0.003, 0.336, and 0.003 mg L–1), caffeic acid (−, 0.005, and 0.005 mg L–1), luteolin (0.003, 0.323, and 0.005 mg L–1), and p-coumaric acid (0.018, 0.015, and 0.027 mg L–1). Forty-five volatile organic compounds were also identified. The sugarcane juice can be commercialized as an alternative to wine as it presents characteristics of an alcoholic fermented beverage.