The increasing demand for structural metals has driven increasingly complex compositions, which bring critical challenges in processing of these materials. Additive manufacturing, also called 3D printing, is a disruptive technology for creating structural materials and components in a single print. In this talk, I will present our recent work on additive manufacturing of compositionally complex alloys (CCAs) with tailored microstructures and properties. Specifically, I will show the potential of leveraging laser additive manufacturing and direct ink writing to produce CCAs such as high-entropy alloys and bulk metallic glass composites with unique microstructures, leading to extraordinary mechanical properties that can extend far beyond those achievable via conventional processing methods. In addition, I will discuss the abundant opportunities enabled by additive manufacturing for high-throughput materials discovery to accelerate the pace of multicomponent alloy design.