Due to their numerous potential applications, the interest for the elaboration of new molecular switch has never stop to grow. Among them, multi-modal systems, where the switching between two different metastable states can be induced by using indifferently several kinds of stimulation, have a special place. In this study, we present our efforts to develop a class of multi-modal systems based on the association of a triphenylamine core with vinylpyrimidine units that exhibits nice acido and electrochromic properties. The most performant ones can present up to three different forms allowing to modulate their absorption and luminescence properties over three discrete levels. In order to provide limitations and outlooks for such systems, their switching behaviors have been rationalized by the help of DFT and TD-DFT calculations.