Opioids should be offered to patients with moderate-to-severe pain related to cancer or active cancer treatment unless contraindicated. Although oral administration of opioids is generally preferable, a parenteral route may be advisable and mandatory in some clinical circumstances. Parenteral administration of opioids may accelerate the achievement of analgesia. The intravenous route fits the need of rapid achievement of analgesia in patients poorly responsive to other opioids and provides a fast analgesia in patients with breakthrough pain, that has a specific temporal pattern requiring a rapid analgesic effect. When the oral route is unavailable for the presence of nausea, vomiting, or dysphagia. the parenteral route is one of the principal options. Opioids have different pharmacokinetic and pharmacodynamic characteristics and should be chosen according to the individual needs. Thus, the knowledge and experience with these routes of administration are mandatory for anesthesiologists committed to cancer pain management.