As computer-aided design and computer-aided manufacturing (CAD/CAM) technologies have matured, three-dimensional (3D) printing materials suitable for dentistry have attracted considerable research interest, owing to their high efficiency and low cost for clinical treatment. Three-dimensional printing technology, also known as additive manufacturing, has developed rapidly over the last forty years, with gradual application in various fields from industry to dental sciences. Four-dimensional (4D) printing, defined as the fabrication of complex spontaneous structures that change over time in response to external stimuli in expected ways, includes the increasingly popular bioprinting. Existing 3D printing materials have varied characteristics and scopes of application; therefore, categorization is required. This review aims to classify, summarize, and discuss dental materials for 3D printing and 4D printing from a clinical perspective. Based on these, this review describes four major materials, i.e., polymers, metals, ceramics, and biomaterials. The manufacturing process of 3D printing and 4D printing materials, their characteristics, applicable printing technologies, and clinical application scope are described in detail. Furthermore, the development of composite materials for 3D printing is the main focus of future research, as combining multiple materials can improve the materials’ properties. Updates in material sciences play important roles in dentistry; hence, the emergence of newer materials are expected to promote further innovations in dentistry.