Radioactive waste management requires planned and systematic actions to provide confidence that the entire system, processes and final products will satisfy given requirements for quality. The characterisation process is dependent on setting clear characterisation objectives and gathering the right information to underpin the decisions that need to be taken to manage the waste safely. This paper reviews experience of characterisation of waste generated from past nuclear activities that were not conducted in compliance consistent with current criteria, or from unexpected situations that were not planned for. This experience shows that the development of a reliable and efficient characterisation and categorisation methodology is a common challenge for such wastes, referred to here as unconventional and legacy (UL) waste. Through the activites of the Nuclear Energy Agency Expert Group on the Characterisation of Unconventional and Legacy Waste (EGCUL), consideration has been given to widely used waste stream characterisation procedures and methods that were originally developed primarily for application in conventional decommissioning work. Although they provide a substantial basis for characterisation, there are various additional factors that commonly need to be taken into account in the case of UL waste. By analysing the challenges and lessons learned from a variety of case studies and other international experience, it has been possible to identify opportunities for adaptations and enhancements to these characterisation methologies, and these are set out and explained. The need for integration of waste characterisation with other aspects of strategic planning for UL waste management is discussed, including characterisation to address any non-radiological hazards.The analysed case studies have also highlighted the importance of developing a robust legislative and regulatory framework in parallel with an appropriate waste infrastructure to treat, store and dispose of UL waste. Finally, the basic features of a UL waste characterisation roadmap are presented, including the interactions within a wider UL waste management programme and key areas for further consideration and possible development. It is anticipated such work can be supported by continued international cooperation.