Our ability to measure and map plant function at multiple ecological scales is critical for understanding current and future changes in Earth's ecosystems and the global carbon budget. Conventional plant functional types (cPFTs) based on a few productivity-related traits have been previously used to simplify and represent major differences in global plant functions, but more recent research has directly focused on the use of functional trait information. Still, sampling limitations have constrained efforts to truly understand the variance and covariance of functional traits globally. Reflectance spectra offer a fast, repeatable, simultaneous measurement of a wide variety of leaf functional traits and could be used to optically define leaf functional types. To evaluate this concept, we measured leaf reflectance from a wide range of species in a diverse set of ecosystems across central and northern California, including observations from multiple individuals, sites, and seasons. Using principal components analysis, we analyzed spectral variation in relation to categorical attributes such as species and cPFTs, as well as to a set of functional trait metrics calculated from the spectra. We found the first three principal components (PCs) to be weakly related to categorical attributes and more strongly related to spectrally-derived functional metrics. Each PC was more strongly associated with different portions of the spectrum and contained different functional information. We applied a hybrid clustering algorithm to the PC coordinates of the observations to define potential optical leaf functional types. Twelve spectral clusters were identified, and these did not correspond directly to either single cPFTs or species. However, each cluster had a unique functional metric profile. Clusters represented both inter- and intra-species and cPFT functional differences driven by taxonomy, trait evolution and environmental responses, demonstrating their value as optical leaf functional types and the value of the clustering approach used here for defining optical types from leaf spectra. Our findings support the notion that cPFTs do not adequately capture differences in leaf function. They demonstrate that spectral measurements can be used to improve both the definition of PFTs as well as our knowledge regarding the covariance of functional traits within these classes.