The structural characteristics of a diverse array of Quercus coccifera canopies were assessed and related to measured and computed light attenuation, proportion of sunlit foliage, foliage temperatures, and photosynthesis and diffusive conductance behavior in different canopy layers. A canopy model incorporating all components of shortwave and longwave radiation, and the energy balance, conductance, and CO2 and H2O exchanges of all leaf layers was developed and compared with measurements of microclimate and gas exchange in canopies in four seasons of the year. In the denser canopies with a leaf area index (LAI) greater than 5, there is little sunlit foliage and the diffuse radiation (400–700 nm) is attenuated to 5% or less of the global radiation (400–700 nm) incident on the top of the canopy. Foliage of this species is nonrandomly distributed with respect to azimuth angle, and within each canopy layer, foliage azimuth and inclination angles are correlated. A detailed version of the model which computed radiation interception and photosynthetic light harvesting according to these nonrandom distributions indicated little difference in whole-canopy gas exchange from calculations of the normal model, which assumes random azimuth orientation. The contributions of different leaf layers to canopy gas exchange are not only a function of the canopy microclimate, but also the degree to which leaves in the lower layers of the canopy exhibit more shade-leaf characteristics, such as low photosynthetic and respiratory capacity and maximal conductance. On cloudless days, the majority of the foliage in a canopy of 5.4 LAI is shaded —70%–90% depending on the time of year. Yet, the shaded foliage under these conditions is calculated to contribute only about one-third of the canopy carbon gain. This contribution is about the same as that of the upper 13% of the canopy foliage. Computed annual whole-canopy carbon gain and water use are, respectively, 60% and 100% greater for a canopy of 5 LAI than for one of 2 LAI. Canopy water-use efficiency is correspondingly less for the canopy of 5 LAI than for that of 2 LAI, but most of this difference is apparent during the cool months of the year, when moisture is more abundant.