The world’s anticipated shortage of fossil fuels and its ever-increasing consumption pattern has led to rise in petroleum prices and increasing greenhouse gas emissions. This has necessitated the search for discovery of alternate green sources of fuel. Over the last few decades, microalgae have been widely studied as a potential source of biofuel and other high value-added compounds such as proteins and antioxidants. However, the scale-up, commercialization and green-synthesis of these microalgal products is hindered by unfavourable economics associated with expensive and multiple-step bioprocessing and the environmental hazards associated with the use of chemicals, especially organic solvents. The use of green solvents such as supercritical fluid, ionic liquids, deep eutectic solvents and switchable solvents in the bioprocessing has been widely investigated by researchers to alleviate the above-mentioned problems. This review summarizes the results of their investigation over the last decade and focuses on the advances and strategies developed to process and purify the microalgal products of interest.