Structured copper-containing MFI-type (Cu-MFI) zeolite catalysts on paper-like sintered stainless fiber (PSSF) were prepared by a secondary hydrothermal synthesis method and resulting in Cu-MFI coating with good relative crystallinity (80.7%), high BET surface area (237.5m2/g) and uniform pore size distribution (2–3nm). The influence of synthesis temperature (120–180°C) and crystalline time (6–48h) on the relative crystallinity and thickness of the MFI coating were investigated by XRD and SEM showing the adjustable coating thickness of SiCuMFI zeolite (1–7μm). Both framework and non-framework (as CuO phase) Cu species were identified for the prepared catalysts by XPS and H2-TPR. Specifically, the framework Cu species were confirmed by FT-IR, Raman and UV-vis spectroscopic analyses, showing the effectiveness of the current method for promoting the incorporation of Cu in the MFI framework. A new impeller was designed to host the developed structured catalysts, which allowed the facile use of the catalyst for the practical application in a batch reactor for water/wastewater treatment. Catalytic tests (using phenol as the model pollutant) showed the outstanding catalytic activity of the developed catalysts (99% conversion after 40min) with negligible Cu leaching (lower than 1mg/L).