The review aimed at analyzing the evidence available on 3D printable materials and techniques used for the fabrication of orthodontic appliances, focusing on materials properties that are clinically relevant. MEDLINE/PubMed, Scopus, and Cochrane Library databases were searched. Starting from an initial retrieval of 669 citations, 47 articles were finally included in the qualitative review. Several articles presented proof-of-concept clinical cases describing the digital workflow to manufacture a variety of appliances. Clinical studies other than these case reports are not available. The fabrication of aligners is the most investigated application of 3D printing in orthodontics, and, among materials, Dental LT Clear Resin (Formlabs) has been tested in several studies, although Tera Harz TC-85 (Graphy) is currently the only material specifically marketed for direct printing of aligners. Tests of the mechanical properties of aligners materials lacked homogeneity in the protocols, while biocompatibility tests failed to assess the influence of intraoral conditions on eluents release. The aesthetic properties of 3D-printed appliances are largely unexplored. The evidence on 3D-printed metallic appliances is also limited. The scientific evidence on 3D printable orthodontic materials and techniques should be strengthened by defining international standards for laboratory testing and by starting the necessary clinical trials.