A method of surfactant-mediated photovoltaic transportation is proposed in this paper, the surfactant (span 80) layers self-assembled at the water-oil and oil-LN interfaces are employed to isolate photovoltaic charges in this method. The reduced electrostatic attenuation, remarkable hydrophobicity, and strong electrical breakdown suppression of the surfactant layers enable the stable and swift transportation of fL-scale aqueous microdroplets using μW-level laser in an oil medium. Three kinds of microdroplet responses to the laser illumination (unresponsive, repulsive and attractive cases) was found. With the increase of surfactant concentration, the driving mechanism can transit from the coulomb repulsion to the dielectrophoretic attraction that facilitates the photovoltaic transportation. Besides, the minimal laser power required for the attractive response was found correlated with the NaCl concentration inside the microdroplet.