Solid-state fluorescent materials were prepared by the annulation of silylated polycyclic aromatic hydrocarbons (PAHs) with internal alkynes catalyzed by [RuH2(CO)(PPh3)(3)]. Single-crystal X-ray analysis revealed that the annulation proceeded through C-H cleavage at the peri-positions and afforded slightly strained six-membered rings containing silicon. In UV-vis absorption and photoluminescence experiments, bathochromic shifts of the annulation product as compared with those of the corresponding substrates were observed.