The issue of sustainability is a growing concern and has led to many environmentally friendly chemical productions through a great intensification of the use of biomass conversion processes. Thermal conversion of biomass is one of the most attractive tools currently used, and pyrolytic treatments represent the most flexible approach to biomass conversion. In this scenario, microwave-assisted pyrolysis could be a solid choice for the production of multi-chemical mixtures known as bio-oils. Bio-oils could represent a promising new source of high-value species ranging from bioactive chemicals to green solvents. In this review, we have summarized the most recent developments regarding bio-oil production through microwave-induced pyrolytic degradation of biomasses.