This article concerns application of cathodoluminescence (CL) spectroscopy to volcanic quartz and its utility in assessing variation in trace quantities of Ti within individual crystals. CL spectroscopy provides useful details of intragrain compositional variability and structure but generally limited quantitative information on element abundances. Microbeam analysis can provide such information but is time-consuming and costly, particularly if large numbers of analyses are required. To maximize advantages of both approaches, natural and synthetic quartz crystals were studied using high-resolution hyperspectral CL imaging (1.2–5.0 eV range) combined with analysis via laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Spectral intensities can be deconvolved into three principal contributions (1.93, 2.19, and 2.72 eV), for which intensity of the latter peak was found to correlate directly with Ti concentration. Quantitative maps of Ti variation can be produced by calibration of the CL spectral data against relatively few analytical points. Such maps provide useful information concerning intragrain zoning or heterogeneity of Ti contents with the sensitivity of LA-ICPMS analysis and spatial resolution of electron microprobe analysis.