Terpyridine-functionalized Ti nanospike electrodes (TiNS-SiTpy) were developed and applied to cyclic voltammetry and amperometry of Ln (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb) ions and mixed Eu (III) + Ln (III) ions in a 0.1 M NaClO4 electrolyte. Electrodeposition was successfully performed over TiNS-SiTpy electrodes, which were fully examined by scanning electron microscopy, X-ray diffraction crystallography, Fourier-transform infrared spectroscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, photoluminescence (PL), and PL decay kinetics. The Gd and Tb ions were found to increase PL intensities with 10× longer lifetimes of 1.32 μs and 1.03 μs, respectively, compared with that of the electrodeposited Eu sample. The crystal phase and the oxidation states were fully examined for the mixed Ln (Eu + Gd and Eu + Tb) complex structures.