Eddy covariance (EC) measurements have greatly advanced our knowledge of carbon exchange in terrestrial ecosystems. However, appropriate techniques are required to upscale these spatially discrete findings globally. Satellite remote sensing provides unique opportunities in this respect, but remote sensing of the photosynthetic light-use efficiency (ε), one of the key components of Gross Primary Production, is challenging. Some progress has been made in recent years using the photochemical reflectance index, a narrow waveband index centered at 531 and 570 nm. The high sensitivity of this index to various extraneous effects such as canopy structure, and the view observer geometry has so far prevented its use at landscape and global scales. One critical aspect of upscaling PRI is the development of generic algorithms to account for structural differences in vegetation. Building on previous work, this study compares the differences in the PRI: ɛ relationship between a coastal Douglas-fir forest located on Vancouver Island, British Columbia, and a mature Aspen stand located in central Saskatchewan, Canada. Using continuous, tower-based observations acquired from an automated multi-angular spectro-radiometer (AMSPEC II) installed at each site, we demonstrate that PRI can be used to measure ɛ throughout the vegetation season at the DF-49 stand (r2 = 0.91, p < 0.00) as well as the deciduous site (r2 = 0.88, p < 0.00). It is further shown that this PRI signal can be also observed from space at both sites using daily observations from the Moderate Resolution Imaging Spectro-radiometer (MODIS) and a multi-angular implementation of atmospheric correction (MAIAC) (r2 = 0.54 DF-49; r2 = 0.63 SOA; p < 0.00). By implementing a simple hillshade model derived from airborne light detection and ranging (LiDAR) to approximate canopy shadow fractions (αs), it is further demonstrated that the differences observed in the relationship between PRI and ε at DF-49 and SOA can be attributed largely to differences in αs. The findings of this study suggest that algorithms used to separate physiological from extraneous effects in PRI reflectance may be more broadly applicable and portable across these two climatically and structurally different biome types, when the differences in canopy structure are known.