Optical fiber oxygen sensors have attractive attentions such as no oxygen consume, thin size, light weight, flexibility, and immunity to electromagnetic interference. Ruthenium (Ru) complexes are known as luminescent materials whose luminescent light is quenched depending on oxygen concentrations when concentrations of Ru complexes are fixed. They emit phosphorescence with the wavelength of around 620 nm as exited light with the wavelength of 450 nm is irradiated into Ru complexes. As a result, phosphorescence is quenched depending on oxygen concentrations. Conventional optical fiber oxygen sensors have employed large core-diameter such as 1000 μm in order to obtain quenching abundantly, hence they have large transmission loss. Therefore, they have little practicability in the case of remote monitoring system, for example undersea explorations. In this paper, we have successfully developed a novel optical fiber oxygen sensor with transmission GI multi-mode fiber whose core diameter is 62.5 μm and cladding diameter is 125 μm. The sensing portion was fabricated on an end of the fiber with porous composite membranes which is made by glass beads and polyallylamine in Layer-by-Layer technique. The composite membranes immobilized Ru complexes. In experiments, in order to investigate characteristics of the number of layers for porous composite membranes, we tested several kinds of sensors having such as 5-, 50- and 125-layers and confirmed phosphorescent intensity and change of phosphorescence against existence of oxygen. As a result, 5-layer and 50-layer sensors showed best sensitivity and reproducibility.