The term “breakthrough cancer pain” (BTcP) was introduced about 25 years ago. Peaks of pain intensity reported in patients with cancer had been invariably examined in the past years, providing relevant information for a better knowledge of this phenomenon and its treatment. The aim of this critical review was to provide the golden rules, namely, the 10 commandments, for a correct diagnostic pathway of BTcP and a consequent personalized pharmacological treatment. These are as follows: 1) assessment of background analgesia, 2) drugs used for background analgesia, 3) BTcP is a frequent phenomenon, 4) characteristics of BTcP, 5) diagnosis of BTcP, 6) continuous assessment, 7) tailored pharmacological treatment of BTcP, 8) selection of BTcP medication, 9) dosing BTcP medications, and 10) education. These steps may help clinicians to recognize and treat BTcP adequately.