Ion flotation process offers a sustainable way to separate and recycle critical metals from industrial wastewaters that often have low concentrations of target metals. There is a high demand for new flotation reagents which are preferentially environmentally friendly. Microbial biomolecules are an attractive alternative and we are exploring various biomolecules in this regards. The use of these biomolecules as flotation reagents in the ion flotation process can be termed as ‘bioionflotation’. This biotechnological approach for metal recovery from low concentrated waters is still dawning and more research is required to improve the selectivity and process efficiency. In this work, marinobactin (a suite of amphiphilic siderophores) was investigated as a flotation reagent for the separation of Gallium (Ga) from synthetic solutions. Amphiphilic nature of these siderophores and metal complexation ability make them an interesting molecule for an application in the flotation process. Single metal flotation test suggested the Ga recovery and marinobactin-Ga complexation in the collected concentrates was confirmed by HPLC. Further, effects of various operating parameters on the metal recovery and selectivity were studied. The flotation results of the mixed metal solutions (containing Ga and As at 1 mM concentration), showed 88% of Ga recovery and 11% of As recovery, at 0.25 mM marinobactin concentration at pH 4 and air flow rate of 20 ml/min. These results provide the basis to fully embrace the potential of novel bio-ion collectors in developing a highly synergistic process of bioionflotation for recovery of critical metals from low concentrated wastewater.