The superconducting gap structure of recently discovered heavy fermion superconductor PrOs4Sb12 was investigated by using thermal transport measurements in magnetic field rotated relative to the crystal axes. We demonstrate that a novel change in the symmetry of the superconducting gap function occurs deep inside the superconducting state, giving a clear indication of the presence of two distinct superconducting phases with twofold and fourfold symmetries. We infer that the gap functions in both phases have a point node singularity, in contrast to the familiar line node singularity observed in almost all unconventional superconductors.