Photoluminescence of plant extract solutions has been investigated for discrimination of plant life forms (grasses, forbs, and shrubs) using principal component analysis (PCA). Clippings from each of six plant species representing three different plant life forms potentially found in the diets of free-ranging herbivores in the Chihuahuan Desert of North America were investigated for possible discernment. These plants included Sporobolus flexuosus (mesa dropseed, a grass), Pleuraphis mutica (tobosa, a grass), Dimorphocarpa wislizenii (spectacle pod, a forb), Sphaeralcea incana (pale globemallow, a forb), Flourensia cernua leaves (tarbush, a shrub), and Atriplex canescens leaves and stems (fourwing saltbush, a shrub). Emission spectra (370-600 nm) from phosphate buffered saline (PBS) extract solutions (pH 2.2, 7.5 and 12.5) were recorded for each plant with excitation at 365 nm. Use of PBS minimized chlorophyll interference. Discernment among plant life forms within these plant species was achieved.