Extravasation is the accidental injection or leakage of fluid into the subcutaneous or perivascular tissues. Some drugs can cause serious injury such as severe tissue injury, necrosis, and etc. Here we report a case of chemical burn by sodium bicarbonate extravasation due to accidental venous puncture during arterial cannulation. A 42-years-old woman has taken emergency laparotomy surgery due to a stab wound to the abdomen. Massive blood loss has developed, and consequently vital signs were unstable and metabolic acidosis has developed. Sodium bicarbonate has administered via a peripheral intravenous line on the dorsal vein of a right hand that runs to the cephalic vein. However, the cephalic vein that runs by the side of the radial artery has punctured accidentally during the attempt of right radial artery cannulation. Second degree superficial and deep chemical burn by sodium bicarbonate extravasation has developed. Skin lesion about 3 × 4 cm2 with erythema and bullae formation has developed. There were no necrotic changes and the digital sensation was intact. Wet dressing and silicon foam dressing were prescribed. After two weeks, she was discharged. Until then, dermis exposure about 1 × 1 cm2 remained although the skin lesions became getting well.