Depending on species, culture, and environmental conditions, microalgae are capable of producing a variety of volatile organic compounds (VOC). Although several commercial uses have been found for microalgae, little is known about the integration of microalgae-based systems applied to utilization of VOCs generated in the process. This chapter presents the biogeneration of VOCs in microalgae-based systems and focuses on the culture conditions, biosynthesis, and industrial applications of these compounds. Regardless of metabolism, the biosynthesis of VOCs occurs through the formation of pyruvate molecules and with the growth conditions of controlled and appropriate microalgae, photosynthetic microorganisms have the capacity to produce volatile compounds desirable with a pleasant perception threshold. Several biosynthetic pathways are involved in the synthesis of VOCs released by microalgae. Microalgae fatty acid derivatives as aldehydes are the most prevalent VOCs, due to their low odor threshold values. Alcohols are one significant chemical class detected in microalgae cultures.