Ecological intensification (EI) is the enhancement of ecosystem services to complement or substitute for the role of anthropogenic inputs in maintaining or increasing yields. EI has potential to increase farming’s environmental sustainability, e.g. reducing environmentally harmful management activities while sustaining yields. EI is based upon ecological processes which in turn are influenced by biodiversity. We review how biodiversity, particularly vascular plant diversity, can regulate ecosystem processes relevant to EI at multiple spatial scales. At an individual plant genotype level, complementarity in functional traits has a direct impact on productivity. At in-field, population level, mixtures of crop types confer resilience to minimize the risk of pest and disease incidence and spread. Scaling up to the field level, a diversity of non-crop plants (i.e. weeds) provides resources necessary for in-field functional processes, both below ground (carbon inputs, decomposition) and above ground (resource continuity for pollinators and natural enemies). At the landscape scale, mosaics of semi-natural and managed vegetation provide buffers against extreme events through flood and drought risk mitigation, climate amelioration and pest population regulation. Overall this emphasizes the importance of heterogeneity across scales in maintaining ecosystem functions in farmland. Major research challenges highlighted by our review include the need: to better integrate plant functional diversity (from traits to habitat scales) into cropping system design; to quantify the (likely interactive) contribution of plant diversity for effective EI relative to other management options; and to optimize through targeted management the system function benefits of biodiversity for resilient, efficient and productive agroecosystems.