Broccoli is a rich source of diverse bioactive compounds, but how their contents are influenced by different growing seasons and variations in broccoli head sizes remains elusive. To address this question, we quantified sixteen known bioactive compounds and seven minerals in broccoli with varying head sizes obtained in two different growing seasons. Our results suggest that the contents of vitamin C, total phenols, carotenoids, and glucoraphanin were significantly higher in samples from the summer–autumn season, showing increases of 157.46%, 34.74%, 51.80%, and 17.78%, respectively, compared with those from the winter–spring season. Moreover, chlorogenic acid is a phenolic compound with relatively high contents among the six detected, while beta-sitosterol is the sterol with relatively high contents. Further, principal component analysis was conducted to rank the comprehensive scores of the profiles of phenolic compounds, phytosterols, and minerals, demonstrating that the broccoli samples grown during the summer–autumn season achieved the highest composite scores. Our results indicate that broccoli heads from the summer–autumn season are richer in a combination of bioactive compounds and minerals than those from the winter–spring season based on the composite score. This study extends our understanding of the nutrition profiles in broccoli and also lays the foundation for breeding broccoli varieties with improved nutrition quality.