To apply titanate nanosheet/decyltrimethlammonium/rhodamine 3B (TNS/C10TMA/R3B) hybrid material with highly luminescent ability to high performance sensor or indicator, spectroscopic properties in the absence and presence of water and/or NH3 vapors were investigated. The TNS/C10TMA/R3B hybrid material exhibited tone change of photoadsorption and photoluminescence in the presence of water vapor. Moreover, this material exhibited remarkable quenching in the presence of NH3 vapor under humid condition. It was found that this quenching was caused by an intramolecular cyclization reaction of incorporated R3B. This photoluminescence intensity decreased with an increase in NH3 concentration. This fact is that the present hybrid material has a high potential for molecular sensor or indicator.