Reported here is a new metal chalcogenide semiconductor with the double-interpenetrated zeolitic nabesite framework, which is constructed by the rare extended spiro-5 units with supertetrahedral clusters serving as building units, Diffetent from the TO4-based simple spiro-5 unit frequently observed in oxide-based zeolites, the extended spiro-5 unit composed of five supertetrahedral T3-InSnS clusters is for the first time observed in the family of open-frame work metal chalcogenides. Such secondary building units finally assemble into a rare NAB topological framework with large external space. In addition, the title semiconductor material also displays good properties in photocurrent response and electrocatalytic oxygen reduction reaction.