We report on the application of a novel technique known as Laser-Induced Breakdown Spectroscopy (LIBS) for remotely detecting and characterizing the elemental composition of highly radioactive materials including spent-fuel residues and High-Level Waste (HLW). Within the UK nuclear industry, LIBS has been demonstrated to offer a convenient alternative to sampling and laboratory analysis of a wide range of materials irrespective of the activity of the material or the ambient radiation levels. Proven applications of this technology include in-situ compositional analysis of nuclear reactor components, remote detection and characterization of vitrified HLW and remote compositional analysis of highly-active gross contamination within a spent-fuel reprocessing plant.