Table olives are essential components of the Mediterranean diet and their consumption is constantly spreading worldwide. However, as there are special concerns regarding their contribution to salt intake, there is a trend to reformulate traditional products via safe interventions. The present work systematically examines the profile of volatile organic compounds (VOCs) in brines during spontaneous fermentation of Spanish-style cv. Chalkidiki green table olives under high (8% w/v) and 50% lower NaCl content using selected combinations of chloride salts (NaCl, KCl, CaCl2) in pilot-scale for two consecutive periods. VOCs were determined by headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry. Changes in population of the dominant microbial groups, pH and titratable acidity values were also investigated using appropriate methods. A total of 56 VOCs were identified, including acids, alcohols, carbonyls, esters, and phenols. A volatilomic approach through multivariate data analysis allowed to explore the links between volatile metabolites, microbial groups and fermentation stages under different NaCl conditions. The evolution of propanoic acid and 2-butanol was intriguing for monitoring a fermentation dominated by lactic acid bacteria under low NaCl conditions, while 3-methyl-1-butanol was indicative of yeast prevalence, arising from seasonal variation and/or high NaCl processing. Furthermore, a sharply increased content of acetic acid at a late stage of fermentation was typical in low NaCl brines. The comprehensive results aided to systematically evaluate the volatile variation in high/low NaCl content brines throughout spontaneous fermentation of Spanish-style cv. Chalkidiki olives and could be beneficial for marker-assisted monitoring of the fermentation processes in the future.