Imaging of cathodoluminescence (CL) emission from carbonate minerals by scanning electron microscopy (SEM) is problematic owing to the slow rate at which CL decays from each point as the electron beam is scanned over an area (the phenomenon of phosphorescence). Using SEM-CL and a newly developed electron probe–based technique of hyperspectral mapping, we have evaluated methods that have been proposed to overcome phosphorescence. With the dwell-time technique, the duration of time that the electron beam is static is increased such that CL emission from a given point makes a negligible contribution to the total signal from subsequent points. The dwell-time required to form sharp SEM-CL images of calcite that has a high intensity of luminescence at orange wavelengths is equal to or greater than 6.4 milliseconds, whereas calcite that luminesces predominantly at ultraviolet to blue wavelengths can be imaged using submillisecond dwell times. By using longer dwell times (> 1000 ms), CL and X-ray spectra can also be acquired from each point to form hyperspectral maps. The limited-wavelength imaging technique employs optical filters to excise slowly decaying long-wavelength emission so that the image is formed only using the more rapidly decaying ultraviolet to blue wavelengths, allowing shorter dwell times to be used. Both techniques have some disadvantages. The main drawback of the dwell-time technique is the long period of time required to acquire high-resolution images whereas the success of limited-wavelength imaging may depend on the sensitivity of the CL detector being used. CL images and emission spectra acquired by hyperspectral mapping also show that there is a nonlinear relationship between luminescence intensity variations at ultraviolet to blue wavelengths and intensity variations at orange wavelengths, indicating that short-wavelength emission is an imperfect proxy for zoning at longer wavelengths. Additionally, we have been unable to identify the controls on spatial variations in the intensity of ultraviolet to blue luminescence, although our data discount Fe2+ concentrations as being the sole determinant. By using hyperspectral mapping in combination with electron-probe microanalysis to obtain CL and X-ray spectra from the same micrometer-sized volume of a material, it is now possible to understand and quantify the controls on activation and quenching of CL in calcite and other minerals such as apatite and zircon.