The effect of physiological maturity at harvest on ripe tomato (Lycopersicon esculentum Mill.) volatile profiles was studied using ripening response time (in days) to 100 μL·L-1 exogenous ethylene treatment as a tool to separate immature-green from mature-green fruit. Electronic nose (EN) sensor array and gas chromatography (GC) analyses were used to document volatile profile changes in tomatoes that required a 1-, 3-, or 5-day ethylene treatment to reach the breaker stage. EN output analysis using multivariate discriminant and canonical analyses classified intact tomato and whole tomato homogenate samples that required 3 or 5 days of ethylene treatment as significantly different (P < 0.01) from those that required only 1 day. The GC aroma profiles from whole tomato homogenate showed that 1-day fruit had significantly higher levels (P < 0.05) of 1-penten-3-one, cis-3-hexenal, 6-methyl-5-hepten-2-one, 2-isobutylthiazole, and geranylacetone when compared to 5-day fruit. Analysis of excised tomato tissues showed that pericarp (including columnella) produced an average 219% greater concentration of the 16 aroma volatiles quantified by GC when compared to locular gel (442 and 203 μL·L-1, respectively). EN analysis concurred with GC by showing greater average Mahalanobis distance between pericarp tissue groupings when compared to locular gel groupings (78.25 and 12.33 units, respectively). Pericarp tissue from the 5-day ethylene treatment showed significantly lower levels of 1-penten-3-one, trans-2-heptenal, 6-methyl-5-hepten-2-one, 2-isobutylthiazole, geranylacetone, and β-ionone compared to the 1- and 3-day treatments, Similarly, locular gel from the 3- and 5-day ethylene treatments had significantly lower levels of 1-penten-3-one, 2-isobutylthiazole, and 1-nitro-2-phenylethane compared to 1-day samples. cis-3-Hexenol in locular gel was the only volatile compound that showed significantly higher levels with increasing ethylene treatment. EN analysis showed greater Mahalanobis distances between 1- and 3-day ethylene samples than between 3- and 5-day ethylene samples (32.09 and 12.90, 24.14 and 6.52, 116.31 and 65.04, and 15.74 and 13.28 units, for intact tomato, whole tomato, pericarp, and locular gel homogenate, respectively).