In this article we report the synthesis of nanoparticles using femtosecond laser ablation with MHz pulse frequency at room temperature in air. Nanoparticles agglomerate by fusion, and form interweaving fibrous structures that show certain degree of self-assembly. It is found that there is a threshold-like pulse frequency at which fibrous nanoparticle aggregates start to form. The growth mechanism can be explained by existing theories regarding nanoparticle formation through femtosecond laser ablation. The threshold pulse frequency is in good agreement with the time to start nanoparticle formation, which has been derived numerically by previous analyses.