Microalgae biomass has garnered significant attention as a renewable energy feedstock and alternative to petroleumbased fuels. The diverse metabolism of green microalgae species additionally provides opportunities for recovery of products for feed, food, nutraceutical, cosmetic, and biopharmaceutical industries. Recently, the concept of using microalgae as part of a biorefinery model has been adopted in place of refinery methods focused on recovering one target product. This has led to producers exploring co-production of high value and high volume products in an effort to improve process economics. With numerous potential products and applications, the biomass source or specific strain must be carefully selected to accumulate extractable levels of the target molecule(s). It is additionally imperative to understand the morphology and metabolism of the selected strain to cost-effectively manage all stages of commercial production. This review will focus specifically on microalgae in the division of Chlorophyta, or green algae and their extracellular matrices (ECM), potential for commercial products, and finally describe a holistic approach for biomolecule extraction and recovery. Additionally, cell disruption and fractionation methods for recovery of biomolecules for commercial products are highlighted along with an alternative method, aqueous enzymatic processing for multiple biomolecule extraction and recovery from green microalgae. An emphasis is placed on connecting the morphological characteristics of microalgae ECM or organelle membranes to implications on separation and purification technologies.