Technological advances in metabolomics, transcriptomics and genomics have facilitated the detection of genes that contribute to diversification in plant secondary metabolism. Statistical tools from molecular population genetics may help in evaluating whether the corresponding genes or genomic regions carry a signature of selection and answering the question of whether novel compounds are 'adaptive'. Gene duplication fuels diversification in plant secondary metabolism and the evolutionary mechanism for adaptation may follow a path of neofunctionalization subsequent to gene duplication, or gene duplication may occur subsequent to--and resolve--an adaptive conflict present in a single ancestral gene sequence. Copyright © 2011 Elsevier Ltd. All rights reserved.