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This study aims to investigate the taste and odor characteristics of broccoli by different thermal processes. For electronic tongue analysis, sourness and umami tastes increased after thermal processing, however, saltiness, sweetness, and bitterness decreased after thermal processing. Among all broccolis, air‐fried broccoli was the highest sourness (6.9) and umami (7.8) tastes, however, saltiness (8.7), sweetness (6.2), and bitterness (10.0) were the highest in the raw broccoli. For electronic nose analysis, a total of 28 volatiles were identified. Among sulfur‐containing compounds, methanethiol and 2,4,5‐tirmethylthiazole were identified as major volatiles in the raw broccoli, however, these volatiles were decreased upon thermal processes. In addition, dimethyl disulfide, 2‐methyl‐3‐furanthiol, and 2‐acetylthiazoline may be generated by thermal processes. In multivariate analysis, the flavor dissimilarity between oven‐heated and microwaved broccolis showed the lowest dissimilarity among all broccolis. Raw broccoli showed the highest dissimilarity among all broccolis. This study is believed to be the first study demonstrating flavors in broccoli by different thermal processing. Novelty impact statement: The present work further investigates the effects of various heating processes, including blanching, oven‐heating, microwave heating, and air‐frying. Thus, this study will be utilized by researchers and food industry that are interested in consuming cooked broccoli. The changes in tastes and odors in thermally processed broccolis were rarely reported. Therefore, this study will be considered worthy that contributes to basic data for further study to characterize flavor and taste in broccoli. [ABSTRACT FROM AUTHOR]