We fabricated a silica optical fiber doped with InP sandwiched in the core and the inner cladding layers by using the conventional modified chemical vapor deposition process. We presented the experimental X-ray analysis on the optical properties and found that compound InP was contained in the fiber core after annealing process. Broadband photoluminescence observed in InP doped fiber was well coincided with those coming from the recombination of deep levels in InP. The occurrence of temperature-dependent photoluminescence both at the lower and room temperature would be related with the localized defects and their confinement in the micro-network structure of Si-O-Si. The Raman spectra reveal that Si-O-In vibration would disorder the silica ring structures and enervate their vibrations. (c) 2009 Elsevier B.V. All rights reserved.