Submerged metal surfaces in marine waters undergo rapid microbial colonization and biocorrosion, causing huge damage to marine engineering facilities and significant financial losses. In coastal areas, an accelerated and particularly severe form of biocorrosion termed accelerated low water corrosion (ALWC) is widespread globally. While identification of biocorroding microorganisms and the dynamics of their community structures is the key for understanding the processes and mechanisms leading to ALWC, neither one is presently understood. In this study, analysis of constructed clone libraries and qPCR assays targeting group-specific 16S rRNA or functional marker genes were used to determine the identity and abundance of putative early carbon steel surface-colonizing and biocorroding microbes in coastal seawater. Diverse microbial groups including 10 bacterial phyla, archaea and algae were found to putatively participate in the surface-colonizing process. Analysis of the community structure of carbon steel surface microbiota revealed a temporal succession leading to ALWC. By extending the current state of knowledge, our work demonstrates the global importance of Alphaproteobacteria (mainly Rhodobacterales), Gammaproteobacteria (mainly Alteromonadales and Oceanospirillales), Bacteroidetes (mainly Flavobacteriales) and microalgae as the pioneer and sustaining surface colonizers that contribute to initial formation and development of surface biofilms. We also discovered Epsilonproteobacteria and the recently described Zetaproteobacteria as putative corrosion-causing microorganisms during early steps of the ALWC process. Hence, our study reports that Zetaproteobacteria may be ubiquitous also in non-hydrothermal coastal seawaters and that ALWC of submerged carbon steel surfaces in coastal waters may involve a highly diverse, complex and dynamic microbial consortium. Our finding that Epsilon- and Zetaproteobacteria may play pivotal roles in ALWC provides a new starting point for future investigation of the ALWC process and mechanism in marine environments. Further studies of Epsilon- and Zetaproteobacteria in particular may thus help with the design of effective corrosion prevention and control strategies.