The dimer and the excimer formation mechanisms of anthracene in NaY zeolitic nanocavities have been studied by using various spectroscopic techniques of Xe-129 NMR, diffuse reflectance, and emission as well as time-resolved fluorescence. Two anthracene molecules adsorb concertedly into a zeolitic supercage to form a ground-state stable dimer. An excited monomer in a singly occupied supercage gives birth to an excimer if another monomer exists in a tetrahedrally connected nearest supercage. An excited monomer forms a nonluminescent ion pair with a monomer in a nearest supercage by transferring an electron within 100 ps. The dark intermediate rearranges to transform into an excimer on the time scale of 400 ps.