Imaging spectroscopy is emerging as a leading remote sensing method for quantifying plant biodiversity. The spectral variation hypothesis predicts that variation in plant hyperspectral reflectance is related to variation in taxonomic and functional identity. While most studies report some correlation between spectral and field‐based (i.e., taxonomic and functional) expressions of biodiversity, the observed strength of association is highly variable, and the utility in applying spectral community properties to examine environmental drivers of communities remains unknown. We linked hyperspectral data acquired by airborne imaging spectrometers with precisely geolocated field plots to examine the spectral variation hypothesis along a temperate‐to‐boreal forest gradient in southern Québec, Canada. First, we examine the degree of association between spectral and field‐based dimensions of canopy tree composition and diversity. Second, we ask whether the relationships between field‐based community properties and the environment are reproduced when using spectral community properties. We found support for the spectral variation hypothesis with the strength of association generally greater for the functional than taxonomic dimension, but the strength of relationships was highly variable and dependent on the choice of method or metric used to quantify spectral and field‐based community properties. Using a multivariate approach (comparisons of separate ordinations), spectral composition was moderately well correlated with field‐based composition; however, the degree of association increased when univariately relating the main axes of compositional variation. Spectral diversity was most tightly associated with functional diversity metrics that quantify functional richness and divergence. For predicting canopy tree composition and diversity using environmental variables, the same qualitative conclusions emerge when hyperspectral or field‐based data are used. Spatial patterns of canopy tree community properties were strongly related to the turnover from temperate‐to‐boreal communities, with most variation explained by elevation. Spectral composition and diversity provide a straightforward way to quantify plant biodiversity across large spatial extents without the need for a priori field observations. While commonly framed as a potential tool for biodiversity monitoring, we show that spectral community properties can be applied more widely to assess the environmental drivers of biodiversity, thereby helping to advance our understanding of the drivers of biogeographical patterns of plant communities.