Microalgae present properties that make them exceptional and a material with high potential. They can generate highly valuable bioactive molecules, which could be traduced into industrial relevance. However, most of these useful compounds are accumulated inside the cells, so their extraction and purification are considered the major bottleneck of the microalgal industry. The conventional methodologies for compound extraction hold some disadvantages, such as elevated costs, low selectivity, reduced extraction yields, high rate of degradation of interest compounds, long treatment times, high energy demands, and harmful environmental impact. The gaps reported for these methods prove that alternative approaches, such as pulsed electric fields, ionic liquids, green solvents, high-pressure processing, and especially the biotechnological approaches (enzymatic-assisted extractions and fermentations), are exciting options to surpass the current drawbacks in the extraction of microalgal added-value compounds. These alternative processing techniques could remove various compounds, increasing the possibility of developing large-scale processes with positive techno-economic balances. The present chapter provides an overview of the novel microalgae used for bioactive compound extraction; it also specifies in detail the current biotechnological strategies and some of the most recent extractive approaches developed to optimize the extraction of the different bioactive compounds from these sources.