The grain aroma is a primary sensory attribute of high-quality rice that contributes a critical impact on consumer preference. Aromatic rice possesses typical volatile compounds released from the grain that discriminates aromatic rice varieties from ordinary ones. These varieties have become more widely appreciated in the current market. Furthermore, recent researches have led to an increase in rice breeding programs focusing on the odour profile to generate high quality aromatic rice cultivars. Therefore, an analytical method for key-marker aroma compounds determination is crucial to facilitate the selection of lines with superior aroma attributes.Using a dynamic HS-SPME system coupled to a GC×GC-TOFMS and multivariate analysis, the aroma chemistry of Indonesian aromatic and non-aromatic rice grains were compared and characterised to define the chemical markers of aroma quality. Sequentially, the analytical method of HS-SPME tandem with GC×GC-TOFMS for the determination of key marker aroma compounds in rice grains were developed and validated. The factors that are most likely to affect the HS-SPME efficiency were evaluated using a 2_III^(5-2) fractional factorial design in conjunction with multi-response optimisation.