A supramolecular complex, [Kpic]n (pic-is picratol, (NO2)3C6H2O-), has been synthesized unexpectedly in acetone solution, and characterized by elemental analysis, IR and X-ray crystallography. In the complex, the K+∶pic-is 1∶1, and one K(Ⅰ) ion is surrounded by six picrate anions, one picrate anion can coordinate to six K(Ⅰ) ions. The coordination number of every potassium atom is eight. Interestingly, the picratol adopts an eight-coordinated ideal mode unreported. CCDC:630627.