This review describes the chemistry of the bacterial biofilms including the chemistry of their constituents and signalling compounds that mediate or inhibit the formation of biofilms. Systems are described with special emphasis, in which quorum sensing molecules (autoinducers) trigger the formation of biofilms. In the first instance, N-acyl-L-homoserine lactones (AHLs) are the focus of this review, whereas the inter-species signal known as furanosyl borate diester and peptide autoinducers used by Gram-positive bacteria are not discussed in detail. Since the first discovery of an AHL autoinducer from Vibrio fischeri a large and further increasing number of different AHL structures from Gram-negative bacteria have been identified. This review gives a summary of all known AHL autoinducers and producing bacterial species. A few systems are discussed, where biofilm formation is suppressed by enzymatic degradation of AHL molecules or interference of secondary metabolites from other species with the quorum sensing systems of communicating bacteria. Finally, the multi-channel quorum sensing system, the intracellular downstream processing of the signal, and the resulting response of whole populations including biofilm formation are discussed for the Vibrio genus that has been extensively investigated.