Microalgae and their metabolites have been an El Dorado since the turn of the 21st century. Many scientific works and industrial exploitations have thus been set up. These developments have often highlighted the need to intensify the processes for biomass production in photo-autotrophy and exploit all the microalgae value including ExoPolySaccharides (EPS). Indeed, the bottlenecks limiting the development of low value products from microalgae are not only linked to biology but also to biological engineering problems including harvesting, recycling of culture media, photoproduction, and biorefinery. Even respecting the so-called “Biorefinery Concept”, few applications had a chance to emerge and survive on the market. Thus, exploiting EPS from microalgae for industrial applications in some low-value markets such as food is probably not a mature proposition considering the competitiveness of polysaccharides from terrestrial plants, macroalgae, and bacteria. However, it does not imply drawing a line on their uses but rather “thinking them” differently. This review provides insights into microalgae, EPS, and their exploitation. Perspectives on issues affecting the future of EPS microalgae are also addressed with a critical point of view.

Biorefinery approaches offer the potential to improve the economics of the microalgae industry by producing multiple products from a single source of biomass. Chromochloris zofingiensis shows great promise for biorefinery due to high biomass productivity and a diverse range of products including secondary carotenoids, predominantly astaxanthin; lipids such as TAGs; carbohydrates including starch; and proteins and essential amino acids. Whilst this species has been demonstrated to accumulate multiple products, the development of an integrated downstream process to obtain these is lacking. The objective of this review paper is to assess the research that has taken place and to identify the steps that must be taken to establish a biorefinery approach for C. zofingiensis. In particular, the reasons why C. zofingiensis is a promising species to target for biorefinery are discussed in terms of cellular structure, potential products, and means to accumulate desirable components via the alteration of culture conditions. Future advances and the challenges that lie ahead for successful biorefinery of this species are also reviewed along with potential solutions to address them.