We report on the formation of submicrometer voids within Sm(DBM)3Phen-doped poly(methyl methacrylate) (PMMA) under multiphoton absorption excited by an infrared laser beam. An ultrashort-pulsed laser beam with a pulse width of 200 fs at a wavelength of 800 nm is focused into doped PMMA. The large changes in refractive index and the fluorescence associated with a void allow conventional optical microscopy and reflection-type confocal microscopy to be used as detection methods. Voids can be arranged in a three-dimensional multilayered structure for high-density optical data storage.