There have recently been new research trends in efficient discrete sampling and optimization. We are organizing this workshop with the goals of 1) syncing up on the latest research progress in discrete sampling and optimization, 2) discussing the limitations of current methods and brainstorming new algorithm paradigms, and 3) connecting to applications in domains such as language/protein modeling, physics simulation, and bio/chemical engineering---where improved techniques for sampling/optimization in discrete space could help---and exploring the gaps between the application's needs and the capabilities of existing methods. We hope this workshop will be an excellent opportunity for presenting and discussing new algorithms and applications with researchers and practitioners within or outside the domain of discrete sampling/optimization.