We investigated femtosecond laser trapping dynamics of silica nanoparticles with different hydrophobic surface properties. We demonstrated that the hydrophobic surface on the silica nanoparticles facilitates mutual association of the nanoparticles in the optical trapping site. Such association of optically trapped nanoparticles is a prerequisite to induce their directional ejection away from the trapping site. The directional ejection of the optically trapped nanoparticles is most probably due to asymmetric three-dimensional ejecting forces generated by the electromagnetic interaction between transient assembly in the focal spot and the incident pulses. These findings provide important insights into the directional ejection of nanoparticles from the trapping site in the femtosecond laser trapping, and this physicochemical phenomenon is controlled by both the trapping laser and material properties.