The study aimed at evaluating the influence of fermented sugarcane molasses ageing on lees and the distillation process used for the production of rums. Molasses were freshly fermented or 3-months lees aged. Batch (PS: Pot Still) or continuous (CS: Coffey Still) distillation was carried out resulting in four different rum distillates. Gas chromatography and 3D-fluorescence enabled to differentiate rum distillates chemical composition according to the distillation process, regardless of the ageing on lees of fermented molasses. Differences in fluorescent PARAFAC components and volatile acids, acetals and carbonyls contents revealed the predominance of the physicochemical processes driven at the liquid-vapor interface of fermented molasses, generated by the distillation systems. Notwithstanding the distilling conditions, the long chain fatty ester content was significantly higher in the 3-months lees aged condition. Multivariate analysis highlighted that CS rum distillates were chemically more homogeneous than those obtained by PS that preserved the lees effect.