This study focuses on the optimisation and characterisation of novel, ORganically MOdified SILicate (ORMOSIL)-based, hybrid sensor films for use in the detection of O-2 on a breath-by-breath basis in human health monitoring applications. The sensing principle is based on the luminescence quenching of the O-2-sensitive ruthenium complex [Ru(II)-tris(4,7-diphenyl-1,10-phenanthroline)], which has been entrapped in a porous sol-gel film. The detection method employed is that of phase fluorometry using blue LED excitation and photodiode detection. Candidate sensor films include those based on the organosilicon precursors, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane and phenyltriethoxysilane. While it has been established previously by the authors that these films exhibit a stable, highly sensitive response to O-2, this study focuses on selecting the material most suited for use in a breath monitor, based on the sensitivity, response time and humidity sensitivity of these films. Key parameters to be optimised include the O-2 sensitivity of the film and the film polarity, i.e. the degree of hydrophobicity. These parameters are directly linked to the precursors used. In this study a n-propyltriethoxysilane-derived O-2 sensor platform was selected as the optimum material for in-breath O-2 analysis due to its short response time, negligible humidity interference and suitable O-2 sensitivity in the relevant range in addition to its compatibility with a single-point calibration strategy.