High-pressure phases IV and V of calcium discovered in 2005 have the highest superconducting transition temperature of 25 K among all the elements; however, their crystal structures have not been determined. From the x-ray powder diffraction data, both Ca IV and V have been found to form unique and complex structures with a coordination number of 7. They were confirmed to be identical to the theoretical models that were recently predicted [Ishikawa, Phys. Rev. B 77 020101(R) (2008)].