Recent experiments on grassland ecosystems have shown that biodiversity can enhance ecosystem processes such as plant biomass production. Functional complementarity is generally regarded as the main class of mechanisms generating these effects of biodiversity on ecosystem functioning. Although intuitively appealing and supported by some data, the complementarity hypothesis has been little explored theoretically using mechanistic approaches. Here, we present a simple dynamical model for a light-limited terrestrial ecosystem to assess the effects of species diversity on light competition and total biomass in plant communities. Our model shows that competitive relaxation (reduction in average light competition intensity) due to differences in foliar architecture among species enhances total plant biomass in mixtures, but that competitive imbalance (generated by the variance of the average light competition intensity experienced by different species) can either reinforce the effect of competitive relaxation or counteract it and contribute to reducing total plant biomass. Thus, complementary resource use is not enough to increase total plant biomass in species-rich communities; competitive balance among species also plays an important role. We propose an operational measure of light-use complementarity using empirical field data on light absorption to test the presence of complementarity in natural plant communities.