The present review will explore the most relevant findings on marine microbial biofilm, with particular attention towards its polysaccharide fraction, namely exopolysaccharide (EPS). EPSs of microbial origin are ubiquitous in nature, possess unique properties and can be isolated from the bacteria living in a variety of habitats, including fresh water or marine environments, extreme environments or different soil ecosystems. These biopolymers have many application in the field of biotechnology. Several studies showed that the biofilm formation is closely related to quorum sensing (QS) systems, which is a mechanism relying on the production of small molecules defined as “autoinducers” that bacteria release in the surrounding environment where they accumulate. In this review, the involvement of microbial chemical communication, by QS mechanism, in the formation of marine biofilm will also be discussed.