A novel polymorph of RbCuCl3 (rubidiumcopper trichloride), denoted epsilon-RbCuCl3, has been prepared by chemical vapour transport (CVT) from a mixture of CuO, CuCl2, SeO2 and RbCl. The new polymorph crystallizes in the orthorhombic space group C222(1). The crystal structure is based on an octahedral framework of the 4H perovskite type. The Rb+ and Cl- ions form a four-layer closest-packing array with an ABCB sequence. The Cu-2+ cations reside in octahedral cavities with a typical [4 + 2]-Jahn-Teller-distorted coordination, forming four short and two long Cu-Cl bonds. epsilon-RbCuCl3 is the most structurally complex and most dense among all currently known RbCuCl3 polymorphs, which allows us to suggest that it is a high-pressure phase, which is unstable under ambient conditions.