Pea is a grain legume crop commonly grown in semi-arid temperate regions. Pea is susceptible to heat stress that affects development and reduces yield. Leaf pigments and surface wax in a crop canopy make the primary interaction with the environment and can impact plant response to environmental stress. Vegetation indices can be used to indirectly assess canopy performance in regard to pigment, biomass, and water content to indicate overall plant stress. Our objectives were to investigate the contribution of leaf pigments and surface wax to heat avoidance in pea canopies, and their associations with spectral vegetation indices. Canopies represented by 24 pea cultivars varying in leaf traits were tested in field trials across six environments with three stress levels in western Canada. Compared with the control non-stress environments, heat stress reduced leaf lamina and petiole chlorophyll a, chlorophyll b, and carotenoid concentrations by 18–35%, and increased leaf lamina chlorophyll a/b ratio, anthocyanin and wax concentrations by 24–28%. Generally, greater leaf pigment and wax concentrations were associated with cooler canopy temperature and high heat tolerance index (HTI) values. Upright cultivars had higher HTI values, whereas the lowest HTI was associated with normal leafed vining cultivars. Vegetation indices, including photochemical reflectance index (PRI), green normalized vegetation index (GNDVI), normalized pigment chlorophyll ratio index (NPCI), and water band index (WBI), had strong correlations with HTI and with heat avoidance traits. This study highlights the contribution of pigments and wax as heat avoidance traits in crop canopies, and the potential application of spectral measurements for selecting genotypes with more heat resistant vegetation.