Performances of LaCoxFe1-xO3 perovskites as catalysts in dry reforming of ethane have been studied. Depending on x, the crystalline structure of the perovskite can be either orthorhombic or rhombohedral. The catalytic activity of the perovskite is tightly linked to its structure. If x ≤ 0.5 the reducing catalytic atmosphere leads to the formation of Co° particles in strong interaction with a LaCoyFe1-y (y<x) remaining oxide. Catalysts with higher Co loading (x>0.5) are more easily reduced during the reactivity tests and lead to the formation of Co° on a bimetallic LaFe perovskite. The catalytic activity strongly increases when the perovskites crystalline structure turns from orthorhombic to rhombohedral.