Despite the improved aesthetics of this type of arch wires, there are differing opinions in the literature about their actual clinical validity because of the problems that may arise during their use in the oral cavity. A systematic review was performed to analyzed studies published over the last 25 years about aesthetic orthodontic arch wires, in order to: analyze the technical characteristics and biotechnological properties, highlight the reliability and long-term effectiveness, and establish which are the most significant physical variables in deterring the clinical efficacy during the orthodontic treatment and hypothesize future developments. A total sample of 24 articles was selected. Although initially the outer coating improves the aesthetic value of the orthodontic arch wire, the wear that characterizes clinical use creates significant changes in surface, mechanical properties, such as sliding and friction, impacting negatively on the biocompatibility and aesthetics. Thermoplastic polymers could represent an excellent alternative and a good future prospect for the production of orthodontic wires characterize by an high aesthetic value and optimum mechanical properties.