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Hollow optical fiber probes are used for remote Raman and infrared spectroscopy. Preliminary experiments using these probes are performed, and the results of the experiments show that the hollow fiber probes are useful for endoscopic measurement of Raman and infrared spectroscopy. As regards to Raman spectroscopy, a hollow fiber probe with a ball lens at the end works as a confocal system. It can, thus, detect the molecular structure of biotissues with a high SNR. Owing to their small diameter, the probes are useful for in vivo noninvasive analysis by using a flexible endoscope. A hollow-fiber probe was also used for remote Fourier transform infrared spectroscopy in the form of an endoscopic measurement of infrared reflectometry spectra inside the body. This measurement was made possible by the high flexibility and durability, nontoxicity, and low transmission losses of the hollow-fiber-based probes.