Vigna unguiculata L. Walp. is an African crop spread worldwide mainly for pulses production. Despite being a neglected and under‐utilized food, cowpea leaves are a rich source of phytochemicals and micronutrients. The aim of the work is to characterize the phytochemical composition of cowpea leaves by an optimized ultrasound‐assisted extraction (USAE) and to compare raw and boiled leaves.A three‐level factorial design (Box‐Behnken) was employed for the optimization of the USAE considering three different parameters (% ethanol, drug‐to‐solvent ratio, and number of cycles). The optimized extracts were characterized by LC‐MS/MS. Finally, leaves were boiled at 100 °C for 30 min to simulate traditional cooking procedures and compared to raw leaves. The best extraction condition was EtOH/H2O 1:2 v/v, drug to solvent ratio 1:47 w/v, and 3 extraction cycles. The phytochemicals identified mainly belong to the family of phenolic acids, flavonoids, terpenoids, and alkaloids. Boiled leaves revealed a significant loss of most phytochemicals and a net decrease of their antioxidant activity compared to the raw ones. The results highlight the potential nutraceutical value of cowpea leaves whilst the impoverishment triggered by traditional consumer habits pushes the need to evaluate alternative cooking procedures helpful in the maintenance of their phytochemical properties.