Titanium (IV) silsesquioxane was occluded in the cavities of a mesoporous silica MCM-41. The material was chemically modified with nickel hexacyanoferrate (III) (named MTTiPNiH) and subsequently characterized by spectroscopic techniques: Fourier Transform Infrared, X-ray Dispersive Energy Spectroscopy, Scanning Electron Microscopy and cyclic voltammetry. The voltammetric studies of MTTiPNiH was obtained using a graphite paste electrode which was possible to observe one well-defined redox pair with formal potential E°′ = +0.53 V attributed to Fe^II(CN)₆ / Fe^III(CN)₆ in the presence of Ni²⁺ ions. As an application, the graphite paste electrode modified with MTTiPNiH was tested for sulphite and dipyrone detection.