Flavor quality is import for determining consumer perception and acceptance of tomato products. In this study, ‘Fendou’ tomato fruit were harvested at six ripening stages and sampled to investigate the development of flavor-relevant compounds during vine ripening. Results showed that upon the initiation of ripening there was an increase in respiration rate and concomitant ethylene evolution that was associated with increased membrane permeability. In accordance with these physiological changes, flavor-relevant compounds demonstrated different expression patterns as fruit ripened, which contributed to ‘red-ripe’ flavor characteristics of red-ripe fruit. Based on correlation analysis between ethylene evolution and the flavor-relevant compounds during ‘Fendou’ tomato ripening and the other researchers’ reports, the activation of System 2-dependent autocatalytic ethylene production plays an important role in the development of most flavor-relevant compounds during tomato vine ripening. Overall, our results suggested that most flavor-relevant compounds that accumulated the most during tomato fruit ripening at red stage could be under ethylene regulation and were among the most important contributors to the ‘red-ripe’ flavor. Due to the development of these compounds, the flavor quality at late ripening stages is different from that of fruit at early ripening stages.