An unusual crystallographic orientation of hexagonal Ru with a 4-fold symmetry emerging in epitaxial MgO/Ru/Co2FeAl/MgO heterostructures is reported, in which an approximately Ru(02-23) growth attributes to the lattice matching among MgO, Ru, and Co2FeAl. Perpendicular magnetic anisotropy of the Co2FeAl/MgO interface is substantially enhanced as compared with those with a Cr(001) layer. The MTJs incorporating this structure gave rise to the largest tunnel magnetoresistance for perpendicular MTJs using low damping Heusler alloys. The 4-fold-symmetry hexagonal Ru arises from an epitaxial growth with an unprecedentedly high crystal index, opening a unique pathway for the development of perpendicular anisotropy films of cubic and tetragonal ferromagnetic alloys.