Stand-off, in-situ, laser induced breakdown spectroscopy (LIBS) offers a rapid, safe, and cost-effective method for discrimination of radioactive waste materials arising during the operation of nuclear plants and from decommissioning activities. Characterisation of waste materials is a critical activity in understanding the nature of the waste, ensuring hazardous material is managed safely and that waste can be segregated for reuse, recycle or sentenced for appropriate disposal. Characterisation of materials, often in hostile environments, requires the ability to remotely differentiate between materials in terms of their chemical composition and radioactivity. This proposition was tested using a case study on nuclear grade graphite. Graphite has been used extensively as a moderator material in many nuclear reactors. Internationally, over 250,000 tons of various nuclear-grade graphite, and graphite-bearing, materials exist. These are a major issue for nuclear decommissioning and radioactive waste management, due to the long half-lives of the associated 14C and 36Cl isotopes. LIBS offers a method for discrimination of nuclear grade graphites and other carbon and non-carbon-bearing wastes. This paper describes the development of a workflow method, including LIBS measurement analysis, for the discrimination of pre-irradiated nuclear ‘Pile Grade A’ (PGA) graphite moderator rod and domestic lumpwood charcoal, which act as surrogates for nuclear grade graphite and other carbon-bearing wastes. A new analysis workflow comprising the examination of spectral characteristics, multivariate analysis and molecular isotopic spectroscopy is proposed to enable rapid segregation of graphite from a heterogeneous waste stream. Enhanced characterisation techniques have the potential to significantly reduce the cost of decommissioning large parts of legacy nuclear generation plants.