Microalgae through photosynthesis can convert atmospheric CO2 into biomass to produce biofuels and high value-added bioproducts. the improvement of the cultivation systems helps in the conversion of gases into biomass and, consequently, increase microalgal productivity. Recently, studies involving the technology of physical adsorption with nanomaterials have shown promising results in increasing the CO2 biofixation by microalgae. Polymeric nanoparticles produced by the electrospraying technique stand out as potential adsorbent materials for CO2 capture due to the high surface area per unit volume formed by many active sites that increase the gas adsorption capacity in a liquid medium. The interactions between plant cells and nanomaterials have been revealed the potential of nanobiotechnology to reduce environmental pollution and contribute to sustainability. Moreover, the development of these methodologies can contribute to the viability of large-scale microalgae cultivations for CO2 mitigation. Based on this, the objective of this review is to address the advances of nanobiotechnology to increase CO2 biofixation by microalgae. The potential of adsorbent nanoparticles developed by the electrospraying technique and the key points for applying it for this purpose are also discussed.