Changes in physicochemical characteristics, substrate depletion, and product formation during fermentation were followed in both brine and olive juice in order to achieve a complete knowledge of fermentation chemistry in Spanish-type green olives. Both spontaneous and controlled fermentations were investigated. Fermentation rate, irrespective of the type of fermentation, was lower in olive juice than in brine, but the main acid products eventually reached equilibrium. Final free acidity remained significantly (p < 0.05) higher, and combined acidity remained lower, in brine than in olive juice in both fermentations, but differences in final pH were not significant in controlled fermentation. Final concentrations of lactic and formic acids were significantly (p < 0. 05) higher, and those of ethanol and succinic acid were lower, in controlled fermentation than in spontaneous fermentation. Butanediol, attributable to Enterobacteriaceae growth, was formed only in the latter case. Calculated carbon recoveries were not significantly (p < 0.05) different in any case, giving a mean of some 78%.