In a variety of industries, Additive Manufacturing has revolutionized the whole design–fabrication cycle. Traditional 3D printing is typically employed to produce static components, which are not able to fulfill dynamic structural requirements and are inappropriate for applications such as soft grippers, self-assembly systems, and smart actuators. To address this limitation, an innovative technology has emerged, known as “4D printing”. It processes smart materials by using 3D printing for fabricating smart structures that can be reconfigured by applying different inputs, such as heat, humidity, magnetism, electricity, light, etc. At present, 4D printing is still a growing technology, and it presents numerous challenges regarding materials, design, simulation, fabrication processes, applied strategies, and reversibility. In this work a critical review of 4D printing technologies, materials, and applications is provided.