This chapter focuses on green analytical chemistry that aims at minimising resources and energy guided by ethical considerations and environmental sustainability. It based on four principles: (1) elimination or reduction of reagents and solvents, (2) reduction of emissions, (3) elimination of toxic reagents, and (4) reduction of labour and energy. These principles underline a need to provide alternative solutions to high-cost sophisticated equipment and promote a rapid shift to a low-cost and readily available instrumentation and analytical solutions with appropriate levels of accuracy, sensitivity, and selectivity. Microalgae is a rich source of bioactives and presents a great challenge to analyse and isolate its content. Many technological advances are tailored to individual components generating unnecessary waste and unsustainable use of resources. In this context, this chapter focuses on most recent published work on the sample preparation and extraction techniques enabling efficient release of value-added chemicals. A use of ‘greener’ solvents such as ionic liquids, super critical carbon dioxide is explored in attempt to compare them to traditional solvents. Most literature concentrates on the cell wall disruption to facilitate the process of releasing target molecules to improve yield and purity. Thus, chapter focuses on eco-friendly approaches and synergistic strategies of combined non-mechanical e.g., thermal, chemical, and enzymatic with mechanical e.g., ultrasonication, electric field, and microwaves treatments. Although life cycle analysis (LCA) is routinely used in many sectors as a measure of ‘sustainability’ it is rarely employed for extractions of bioactives. This chapter also explores a ‘suitability’ of LCA approach in the context of microalgae.