In the presented work, titanosilicate with the MWW structure (Ti-MWW) was hydrothermally synthesized using boron and titanium precursors, with piperidine as a structure-directing agent. The resulting layered zeolite precursor, with a Si/Ti molar ratio of 50, was treated in an HNO₃ solution to remove extraframework Ti and B species. The acid-modified zeolite was functionalized with transition metal cations (Cu²⁺, Fe²⁺, Mn²⁺) and trinuclear oligocations (Fe(3) and Mn(3)). The application of this catalytic system is supported by the presence of titanium in the catalytic support structure—similar to a commercial system, V₂O₅–TiO₂. The obtained samples were characterized with respect to their structure (P-XRD, DRIFT), textural parameters (low-temperature N₂ sorption), surface acidity (NH₃-TPD), transition metal content (ICP-OES) and form (UV–vis DRS) as well as catalyst’s reducibility (H₂-TPR). Ti-MWW zeolite samples modified with transition metals were evaluated as catalysts for the selective catalytic reduction of NO with ammonia (NH₃-SCR). The effective temperature range for the NO conversion varied depending on the type of active phase used to functionalize the porous support. The catalytic performance was influenced by transition metal content, its form, and accessibility for reactants as well as interactions between the active phase and titanium-containing support. Among the catalysts tested, the copper-modified Ti-MWW zeolite showed the most promising results, maintaining 90% NO conversion rates across a relatively broad temperature range from 200 to 325 °C. This catalyst meets the requirements of modern NH₃-SCR installations, which aim to operate in the low-temperature region, below 250 °C.