Single crystals of trigonal 3R-CuCrO2 were grown from K2Cr2O7 and CuO by a flux decompn. method. A new metastable hexagonal phase 2H-CuCrO2 was prepd. by quenching the trigonal crystals from 1100 Deg to room temp. X-ray crystal data: for trigonal 3R-CuCrO2, space group R.hivin.3m, a 2.9734(3) .ANG. c 17.100(4) .ANG.; for hexagonal 2H-CuCrO2, space group P63/mmc, a 2.970(1) .ANG., c 11.400(1) .ANG.. A model of the atom shifts occurring during the 3R-2H structural phase transition is presented. During the transformation parts of the layered structure do not change. In other regions atom displacements up to 1.72(1) .ANG. occur. The phase transition unites a first-coordination reconstructive transformation and a second-coordination distortional transformation.