Cathodoluminescence (CL) provides a sensitive analytical probe of the near-surface region of insulating materials, and some new examples of the strengths of the technique are presented using recent data from the University of Sussex. Analysis of float glass shows that by spectral and lifetime resolved data it is possible to separate the emission bands from excitonic, intrinsic imperfections, and impurities in various valence states, as a function of their depth beneath the surface. Correlation of the CL data with those from Mossbauer, ion beam and other analyses then provides the basis for models of the defect sites. CL from a second glass, ZBLAN, reveals the presence of microcrystallites and growth defects, and the work underpins confidence in the high purity gas levitation method of ZBLAN production. New results on CL of wavelength shifts with crystal field of Mn in carbonates are presented, and of Nd emission from Nd:YAG. The effects are directly linked to surface damage and dislocations caused by sample preparation steps of cutting and polishing. Methods to minimise the damage, by furnace or pulsed laser annealing, and chemical routes, are mentioned. Such surface preparation damage has a profound effect on all CL monitoring, whether for fundamental studies or mineralogical applications. Finally, a route to eliminate such problems is demonstrated, with consequent improvements in luminescence, transmission and laser performance of surface waveguides. The implications of improved surface quality range widely from mineralogical CL imaging through improved photonic materials and epitaxial growth to elimination of surface damage, and additional information.