Hydrofluoric acid (HF) is a colorless corrosive acid used in different industrial branches. Exposure to HF typically results from spills, and most often the hand or fingers are involved. Tissue damage through cutaneous HF exposure occurs through corrosive burns due to the free hydrogen ions and through skin penetration of the fluoride ions, causing a depletion of calcium in the deep tissue layers, ultimately leading to cell death and tissue necrosis. Treatment of HF burns consists of thoroughly flushing the exposed area with water and applying calcium gluconate gel to the skin. If topical treatment does not suffice, subcutaneous injections, as well as intravascular—both intravenous and intra-arterial—calcium gluconate therapy, have been advocated. We report for the first time a case of HF burn of the hand and digits associated with vasospasm. Pain and vasospasm were successfully treated by repeated intra-arterial calcium gluconate injection. We conclude that intra-arterial calcium gluconate injection is a successful and well-tolerated therapy for HF burn associated with Raynaud’s syndrome. Intra-arterial injection allows for well-controlled delivery of therapy as well as assessment of the vascular status.