A new type of blue-light-emitting ultralong [Cd(L)(TeO3)] (L=ethylenediamine, diethylenetriamine) nanofibre bundle has been synthesised under reflux in a mixed solvent media. Inorganic Cd(TeO3) layers are assumed to exist in the structures and are connected by the organic amine molecules through the coordination between nitrogen atoms and cadmium ions. The composition and formulae of these hybrid materials, based on the proposed structures, have been identified through element analysis (EA), thermal gravity analysis (TGA) and energy dispersive spectra (EDS). The thermal stabilities and optical properties of these nanofibre bundles have been investigated. Thermal decomposition of [Cd(en)(TeO3)] (en=ethylenediamine) and [Cd(DETA)(TeO3)] (DETA=diethylenetriamine) at 450 °C allowed the formation of a mixture of CdTe and Cd(TeO3) phases, and a pure CdTe phase, respectively. In addition, this new kind of hybrid bundle, which demonstrates blue emission, was found to be sensitive to acids, and the emission intensity is strongly dependent on the acidity of the solutions, implying that these hybrid nanofibre bundles could be potentially applied as acid sensors.