Herein, we present the first lithium difluorophosphate LiPO2F2 exhibiting a unique polytetrahedral microporous architecture. The unique fluorine coordination environments and interlaced [LiO2](3-) straight chains give rise to the neutral pore framework with a 10- membered ring channel along the crystallographic c axis. A variety of measurements have been adopted to systemically characterize LiPO2F2. This work contributes to the structural and functional diversity of phosphate chemistry by the exploration of fascinating difluorophosphates.