Biohydrogen is a plausible alternative fuel solution for the contemporary issues regarding global warming and the steadily increasing greenhouse gas emissions, because of its high energy content and carbon-free combustion properties. Hydrogen does not exist in its natural state and the current hydrogen production technologies (steam methane reforming, water splitting) are energy-intensive, accompanied by a huge carbon footprint. Dark fermentative hydrogen production by anaerobic hydrogen-producing bacteria is a green, sustainable and emission-free pathway for hydrogen production. Microalgal biomass is considered as the third generation biofuel feedstock and is receiving academic and industrial research attention for its carbon sequestration abilities. This review discusses in detail about the pretreatment methods that could be adapted for microalgal biomass for effective biohydrogen production. Microalgal cell wall structure and the associated polymeric carbohydrates that offer certain recalcitrance are critically analyzed and future research perspectives are presented.