Positive effects of biodiversity on ecosystem function are described from an increasing number of systems, but the underlying mechanisms frequently remain elusive. A truly predictive understanding of biodiversity-ecosystem function relationships requires the a priori identification of traits conferring specific (and possibly complementary) functions to individual species. Although planktonic organisms are responsible for approximately half of the world's primary production, few studies have reported on the relationship between phytoplankton biodiversity and planktonic primary production. We argue that taxon-specific differential equipment with photosynthetically active pigments provides a biochemical mechanism of resource use complementarity among phototrophic microorganisms, enabling more diverse communities to more completely harvest the light spectrum. In line with this, more diverse phytoplankton communities showed higher pigment diversity, higher biomass-specific light absorbance, and higher rates of primary production and biomass accrual.