Recent advances in the precision and accuracy of the optical techniques required to measure luminescence permit the nondestructive analysis of solid geologic samples such as speleothems (secondary carbonate deposits in caves). In this paper we show that measurement of speleothem luminescence demonstrates a strong relationship between the excitation and emission wavelengths and both the extent of soil humification and mean annual rainfall. Raw peat with blanket bog vegetation has the highest humification and highest luminescence excitation and emission matrix wavelengths, because of the higher proportion of high-molecular-weight organic acids in these soils. Brown ranker and rendzina soils with dry grassland and woodland cover have the lowest wavelengths. Detailed analysis of one site where an annually laminated stalagmite has been deposited over the past 70 yr during a period with instrumental climate records and no vegetation change suggests that more subtle variations in luminescence emission wavelength correlate best with mean annual rainfall, although there is a lag of ∼10 yr. These results are used to interpret soil humification and climate change from a 130 ka speleothem at an upland site in Yorkshire, England. These data provide a new continuous terrestrial record of climate and environmental change for northwestern Europe and suggest the presence of significant variations in wetness and vegetation within interglacial and interstadial periods.