Tremendous advances in nanoscience have been made since the discovery of fullerenes. However, the short timescale of the growth process and high-energy conditions of synthesis result in severe constraints to investigation of the mechanism of fullerene formation. In this work, we attempted to reveal the formation process by analyzing the variation in the yield of fullerenes under different conditions. Experiments and theoretical analysis show that the formation of fullerenes could be affected by the addition of polycyclic aromatic compounds. It is proposed that the formation of C-60 during arc-discharge synthesis is fragment assembling, while the yield of C-2m (m=35, 38, 39) is strongly enhanced by building-block splicing. In addition, several features of the building blocks are put forward to predict the extent of their influence to the formation of larger fullerenes C-2n (n >= 42). This work not only provides essential insight into the formation process of fullerenes, but more importantly also paves the way to improving the yield of larger fullerenes selectively.