We report the ab initio structure solutions of two solvent containing potassium phenoxides by high-resolution powder X-ray diffraction. Both compounds are of interest for the classification of the mechanism of Kolbe-Schmitt type reactions. C6H5OK . 2C(6)H(5)OH crystallizes in space group Abm2, Z = 4, with unit cell parameters a = 10.12458(4) Angstrom, b = 21.2413(1) Angstrom, c = 7.89784(3) Angstrom. C6H5OK . 3C(6)H(5)OH crystallizes in space group Pbca, Z = 8, with unit cell parameters a = 22.7713(1) Angstrom, b = 25.4479(2) Angstrom, c = 7.75549(4) Angstrom. Both compounds show polymeric zigzag chains (1[)(infinity)K([6])O(2)([2])O([1])pi(phenyl)([1])] aligned along thr c-axis. The coordination of the potassium ions is similar for both compounds. They lie at the center of distorted octahedra of five oxygen atoms and one phenyl ring, which donates its pi electrons. The distortion decreases as the number of free phenol increases.