The titanium species and structure-performance relationship in boron-free Ti-MWW zeolite have been thoroughly studied by 244 nm excited UV resonance Raman spectroscopy for the first time. It was surprisingly found out that acid treatment not only removed a part of the dominant non-framework TiOm (m = 5, 6) species but also made most of them transformed into TiO4 species, which has never been reported before. Interestingly, acid treatment of as-synthesized and directly calcined Ti-MWW resulted in the formation of active framework TiO4 species and inactive TiO4 species in amorphous SiO2 matrix, respectively. Only the samples obtained from acid treatment of as-synthesized Ti-MWW and subsequent calcination showed catalytic activity in 1-hexene epoxidation. Importantly, despite higher Si/Ti ratio, framework Ti(OSi)(4) species-dominant Ti-MWW showed better catalytic performance than the relatively hydrophilic framework Ti(OSi)(3)OH species-dominant one. These understandings would be beneficial for further study of Ti-MWW and development of highly efficient titanosilicate zeolites. (C) 2017 Elsevier Inc. All rights reserved.