Numerous studies exploring the link between daily commuting and mental well-being have primarily relied on cross-sectional designs and self-reported surveys. These methods often limit causal inference and are prone to recall bias. This study adopts a novel approach by utilizing timestamped stress level data (objective) and experience sampling of moods (subjective) to assess the varied stress responses triggered by daily commuting. Our aim is to reexamine the effects of daily commuting on mental well-being, with a particular focus on evaluating how subjective (self-reported moods) and objective (biosignal data) measurement techniques capture these psychological and physiological responses differently. We involved 203 employees from Beijing, who wore portable smartwatches over a week. Throughout five working days, we conducted three random experience sampling surveys daily to collect real-time mood data. Initial analysis visualized the relationships between stress levels, moods, and commuting characteristics such as duration, mode, and timing. Subsequent analysis using mixed-effects models quantified the impacts of these commuting attributes on stress and mood. Our findings reveal that commute duration and mode significantly affect both mood and stress during commuting. Specifically, longer commutes are associated with poorer moods but surprisingly, lower stress levels. Regarding commuting modes, taking the bus and bicycling were found to enhance moods relative to traveling by car. Conversely, walking and cycling appeared to elevate stress levels the most, while shuttle bus use correlated with the lowest stress levels. Our study also highlights a discrepancy between physiological stress, as measured by biosignal technology, and psychological stress, as reported in surveys. This discrepancy underscores the complexities of measuring mental well-being and enriches the ongoing discussion about the intricate relationship between daily commuting and mental health.