Acenes have long been the subject of intense study because of the unique electronic properties associated with their π-bond topology. Recent reports of impressive semiconductor properties of larger homologues have reinvigorated research in this field, leading to new methods for their synthesis, functionalization, and purification, as well as for fabricating organic electronic components. Studies performed on high-purity acene single crystals revealed their intrinsic electronic properties and provide useful benchmarks for thin film device research. New approaches to add functionality were developed to improve the processability of these materials in solution. These new functionalization strategies have recently allowed the synthesis of acenes larger than pentacene, which have hitherto been largely unavailable and poorly studied, as well as investigation of their associated structure/property relationships.