The complexes 1-4 of cyclobutanocucurbit[5]uril (CyB₅Q[5]) with Na⁺/K⁺ have been synthesized and characterized by single-crystal X-ray diffraction. The results show that although the inorganic salts are used when the cations are the same and the anions are different, in complex 1, Na⁺ closes one port of CyB₅Q[5] through Na—O seven coordination bonds to form a molecular bowl; in complex 3, Na⁺ completely closes the two ports of CyB₅Q[5] to form a molecular capsule with six Na—O coordination bonds; in complexes 2 and 4, the two ports of CyB₅Q[5] are completely closed to form K—O coordinated molecular capsules, but the K⁺ of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated. and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.