Development of selective cataluminescence (CTL) sensors toward volatile organic compounds (VOCs) is of great importance to environmental analysis and daily chemicals safety. Although some reports for the determination of VOCs based on CTL have been reported, part of them suffered relatively low selectivity because of their high sensitivity toward interferents. In this study, mesoporous TiO2 nanoparticles have been exploited to detect diethyl ether with the usage of a 440nm bandpass filter. The proposed method showed high selectivity toward diethyl ether over other VOCs, such as acetaldehyde, acetone, butanone and butanol, etc. Such a high selectivity was majorly attributed to the difference of CTL emission profiles of various VOCs reaction intermediates, and only diethyl ether exhibited strong CTL emission at about 440nm. Under the optimal conditions, diethyl ether could be detected ranging from 2.0 to 50.0mM. Furthermore, the practical application of this proposed CTL sensor for diethyl ether was validated with artificial samples and commercial perfumes. In general, such a simple method with high selective detection through controlling detection range could be extended to other analytes.