Various approaches to understand and make use of the variable chlorophyll (Chl) fluorescence emission spectrum and fluorescence ratio are reviewed. The Chl fluorescence of leaves consists of two maxima in the red (near 685-690 nm), and far-red region (near 730-740 nm). The intensity and shape of the Chl fluorescence emission spectrum of leaves at room temperature are primarily dependent on the concentration of the fluorophore Chl a, and to a lower degree also on the leaf structure, the photosynthetic activity, and the leaf's optical properties. The latter determine the penetration of excitation light into the leaf as well as the emission of Chl fluorescence from different depths of the leaf. Due to the re-absorption mainly of the red Chl fluorescence band emitted inside the leaf, the ratio between the red and the far-red Chl fluorescence maxima (near 690 and 730-740 nm, respectively), e.g., as F690/F735, decreases with increasing Chl content in a curvilinear relationship and is a good inverse indicator of the Chl content of the leaf tissue, e.g., before and after stress events. The Chl fluorescence ratio of leaves can be applied for Chl determinations in basic photosynthesis research, agriculture, horticulture, and forestry. It can be used to assess changes of the photosynthetic apparatus, developmental processes of leaves, state of health, stress events, stress tolerance, and also to detect diseases or N-deficiency of plants.