Temporal variations in cancer pain intensity are highly prevalent, and are often difficult to manage. However, the phenomenon is not well understood: several definitions and approaches to classification and bedside assessment of cancer breakthrough pain (BTP) have been described. The present study is a systematic review of published literature on cancer BTP to answer the following questions: which terms and definitions have been used; are there validated assessment tools; which domains of BTP do the tools delineate, and which items do they contain; how have assessment tools been applied within clinical studies; and are there validated classification systems for BTP. A systematic search of the peer-reviewed literature was performed using five major databases. Of 375 titles and abstracts initially identified, 51 articles were examined in detail. Analysis of these publications indicates a range of overlapping but distinct definitions have been used to characterize BTP; 42 of the included papers presented one or more ways of classifying BTP; and while 10 tools to assess patients' experience of BTP were identified, only 2 have been partially validated. We conclude that there is no widely accepted definition, classification system or well-validated assessment tool for cancer-related breakthrough pain, but there is strong concurrence on most of its key attributes. With further work in this area, an internationally agreed upon definition and classification system for cancer-related breakthrough pain, and a standard approach on how to measure it, hold the promise to improve patient care and support research in this poor-prognosis cancer pain syndrome.