Many nociceptive, inflammatory, and neuropathic pathways contribute to perioperative pain. Although opioids have long been a mainstay for perioperative analgesia, other non-opioid therapies, and dexmedetomidine, in particular, have been increasingly used as part of a multimodal analgesic regimen to provide improved pain control while minimizing opioid-related side effects. This article reviews the evidence supporting the preoperative, intraoperative, and postoperative efficacy of dexmedetomidine as an adjuvant, and the efficacy of intravenous, spinal canal, and nerve block analgesia with dexmedetomidine for perioperative acute pain treatment. While there have not been any large-scale clinical trials conducted, the current body of evidence suggests that dexmedetomidine is suitable for use as an adjuvant analgesic at all perioperative stages. However, there are potential adverse effects, such as hypotension and bradycardia, which must be taken into consideration by clinicians.