We report a comprehensive study of the self-assembly of a diindenoperylene (DIP) monolayer on Au(111)single crystals exploiting different electron probes ranging from STM and LEED to photoelectron spectroscopyand NEXAFS. By this multitechnique approach, we obtain a full picture of the crystallographic and electronicstructure of the DIP layer as well as an insight into the assembly process and the role of the DIP-Auinteractions. We contrast these experimental findings with theoretical calculations.