In this work, we synthesized a series of new 9,10‐dihydro‐2H,8H‐chromeno[8,7e][1,3]oxazine‐2‐on derivatives which incorporate isobornylcoumarin and 1,3‐oxazine moieties. A structure‐antioxidant activity relationship was analyzed. A comparative evaluation of their radical scavenging activity, antioxidant and membrane‐protective properties was carried out in test with DPPH, as well as on the models of Fe2+/ascorbate‐initiated lipid peroxidation and oxidative hemolysis of mammalian red blood cells. The results suggest that all the obtained coumarin[1,3]oxazine derivatives of 7‐hydroxy‐6‐isobornyl‐4‐methylcoumarin are capable of exhibiting antioxidant activity in various model systems. Compound 7 with a phenyl fragment, combining high radical scavenging activity and the ability to inhibit Fe2+/ascorbate‐initiated peroxidation of animal lipids in a heterogeneous environment, also proved to be the most effective membrane protector and antioxidant in the model of H2O2‐induced erythrocyte hemolysis.