Recently, metal-organic frameworks (MOFs) composed of sulfur secondary building units (sulfur-SBUs) have attracted significant attention as unique electronic materials with high conductivities and photo- and electrocatalytic properties. Herein we report the crystal structure of KGF-1, an example of a Pb-MOF composed of three-dimensionally extended sulfur-SBUs that displays molecular sieving behavior, visible-light absorption, and a semiconductor band structure and is a hydrogen-evolution photocatalyst.