Microalgae have found commercial applications as natural sources of valuable macromolecules, including carotenoids, long-chain polyunsaturated fatty acids, and phycocolloids. As photoautotrophs, their simple growth requirements make them attractive for bioprocesses aimed at producing high added-value compounds that are in large demand by the pharmaceutical market. A few compounds synthesized by microalgae have indeed proven to possess anti-inflammatory, antiviral, antimicrobial, and antitumoral features; astaxanthin, a known antioxidant produced by Haematococcus pluvialis, is an illustrative example with important anti-inflammatory and antitumoral roles. From a chemical standpoint, several such compounds are polysaccharides or long chain fatty acids, where the latter can be either saturated or unsaturated. Additionally, their chemical structures are often atypical, whereas their concentrations can exceed those found in many other natural sources. The productivity and biochemical composition of microalgae depend strongly on the mode of cultivation, medium composition, and nutrient profile. Consequently, numerous efforts aimed at elucidating the practical impacts of the aforementioned parameters have been developed. This review accordingly covers the knowledge produced in the last two decades on the uses of microalgae to obtain physiologically active compounds, and on the optimization of the underlying production and purification processes. It also identifies major gaps and opportunities in this field that should be addressed or exploited in the near future. (C) 2011 American Institute of Chemical Engineers Biotechnol. Prog., 27: 597-613, 2011