The maxillary nerve block (MNB) is a local anaesthetic technique used in dentistry and oromaxillofacial surgery, with recent popular use for minimising adverse reactions during rhinoscopy. A modified approach via the infraorbital foramen using an intravenous catheter has been recently described in the veterinary literature to minimise potential nerve block associated complications. This case report describes inadvertent arterial catheterisation using the aforementioned technique in a 5.4-kg, 9-year-old male neutered Maltese terrier cross that was presented for diagnostic workup of a chronic cough that had recently worsened. To the authors’ knowledge, this is the first case report of such a complication. It is recommended for veterinary practitioners to be aware of accidental arterial puncture and catheterisation whenever a modified infraorbital approach to the MNB is performed in order to facilitate rapid intervention and management.