Exogenous superoxide dismutase (SOD) or catalase did not modify isolated cat middle cerebral arterial basal tone. Catalase but not SOD reduced ACh relaxation. 2. H2O2 induced endothelium-independent relaxation which was abolished by catalase. 3. 3-Amino-1,2,4-triazole (AT) evoked endothelium-dependent contractions and diminished ACh relaxation. 4. Diethyldithio carbamic acid (DETC) induced endothelium-independent relaxation and did not modify ACh vasodilatation. 5. ACh relaxation of cat isolated pulmonary arteries was unaffected by SOD, catalase or AT, and diminished by DETC. 6. Endothelial catalase but neither SOD nor superoxide anions is involved in EDRF cerebral vasodilatation and H2O2 participates in ACh relaxation. In pulmonary arteries, only endothelial SOD activity plays a role.