Four oligomeric triarylamine compounds (diamine 1a, triamine 1b, tetramine 1c and pentamine 1d) were prepared and characterized by 1H NMR, mass spectrometry and elemental analysis. The combined results of cyclic voltammetry, square-wave voltammetry and UV–vis–NIR spectroelectrochemistry, as well as density functional theory, reveal that compounds 1a–1d display two to five steps of oxidation processes, respectively, and the ΔE1/2 and Kc values were still remarkable for the relatively long pentamine, though they all decreased with an increase of the triphenylamine unit. These four compounds all exhibit fascinating redox-tuned multiple NIR absorption characteristics, and a completely reversible multicolor electrochromism for each of them could be synchronously realized. The associated mono-cationic [1a]+–[1d]+ could be classified as moderately-coupled Robin–Day class II mixed-valence systems, which could be stabilized by spin delocalization over at least two adjacent amine units.