Consumer awareness of broccoli's unusual color, rich flavor, and concentration of desired phytochemicals has led to a steady increase in consumption in recent years. However, its short shelf‐life, which is linked with quick discoloration and degeneration after harvest, limits industrial production and marketing. The effect of pre‐harvest salicylic acid (SA) and calcium chloride (Ca) and their combination on the post‐harvest quality of broccoli during storage (5 ± 1°C) was explored in this study. The foliar spray treatments reduced weight loss of broccoli head during storage. At the end of storage, Ca (2%) alone and in combination with SA (0.01%) significantly maintained the chlorophyll concentration rather than control. The total phenols, flavonoid, and antioxidant capacity of the Ca (2%) + SA (0.01%) treated samples was significantly greater than the control. SA (0.01%) alone or in conjunction with Ca (2%), showed higher catalase (CAT) activity; however, Ca (1%), alone or in combination with SA (0.01%), showed higher peroxidase (POD) activity. Generally, the marketability of the treated broccoli was significantly greater than the control at the end of storage. Based on these findings, we believe Ca (2%) + SA (0.01%) improves the antioxidant system, delays chlorophyll degradation, and extends the shelf life of broccoli heads stored at 5 ± 1°C. It is proposed that the green color, marketability, and nutrient content of broccoli during postharvest handling and storage can be retained longer by foliar application of this treatment. Practical applications Broccoli (Brassica oleracea L. Italaia) is a widely‐consumed floral green vegetable due to its high content of nutrients and bioactive compounds. However, after harvest, florets rapidly senesce and suffer from yellowing which affects the quality of broccoli. The senescence of post‐harvest broccoli is characterized by fresh weight loss, chlorophyll degradation, and a significant reduction in nutritional content. Therefore, preventing the decline in the quality of harvested broccoli is essential to maintain its economic and nutritional value. The results of this study showed that pre‐harvest foliar application of Ca (2%) + SA (0.01%) with delayed weight loss, chlorophyll degradation, preservation of antioxidant compounds, and increased enzyme activity has a positive effect in maintaining broccoli heads quality during cold storage.