A fiber-optic based spectral cathodoluminescence (CL) system has been successfully installed on a variable pressure “environmental” scanning electron microscope (ESEM). The fine size of the fiber (50 μm) has been found to require careful alignment. To provide this alignment, a simple X–Y translator has been used. The aligned fiber exhibits high efficiency and the system has recorded spectra at up to 3 million “counts” per sec on strongly cathodoluminescent doped yttrium aluminium garnet (YAG) samples, at 30 kV and ˜3 nA. A resolution of 3 nm [full width half maximum (FWHM)] at 621 nm has been measured from a red laser diode spectrum, on the ESEM column. A range of uncoated materials has been measured to characterize the CL system; these materials ranged from strongly luminescent YAG to weakly luminescent polymers. Wellcharacterized doped zircons have also been investigated. These data suggest that the previously reported intrinsic peak from zircon is a consequence of high-beam currents.