Ti-MWW is an important member of Ti-containing zeolites employed as heterogeneous catalyst in the ammoximation reaction. Despite the industrial prevalence of Ti-MWW catalysts, the development of more active variants is often hampered by the lack of characterization methods able to track transformations and interplay between a multitude of species. This challenge is exacerbated by the introduction of secondary metals, such as Zn, which allows to significantly enhance catalytic performance. Hence, we set out to employ an array of characterization methods, featuring microscopy and various spectroscopic techniques, enabling a more accurate handle on these changes. Thereby we find that the promotional role of Zn is closely linked to its healing of hydrophilic silanol nests, while simultaneously generating small TiOx clusters. These changes are accompanied by Ti weight loading dependent modifications of the extra-framework TiO2 and formation of Zn species. Overall, our study highlights the interplay between a plethora of species, enabling the assessment of different species, and a more rational development of post-modification of Ti-containing zeolites.