Potassium complexes are starting to gather more and more interest from academia and industry because of their intriguing application possibilities. Novel adducts of potassium hexafluoroacetylacetonato [K(hfa)] with polyethers (monoglyme, diglyme, triglyme, and tetraglyme) were synthesized through a single step reaction and characterized through FT‐IR spectroscopy as well as 1H and 13C NMR spectroscopy. Single crystal X‐ray diffraction studies enabled the identification of fascinating K coordination polymeric networks.