In superconducting spin valves of the type S/F1/N/F2 or F1/S/F2 with a superconducting layer S, two ferromagnetic layers F1 and F2, and a normal metallic layer N, the superconducting transition temperature T S depends on the relative magnetization direction of the ferromagnetic layers F1 and F2. The difference of the transition temperature ⌬T S = T s AP − T s P with the magnetization direction of F1 and F2 either antiparallel or parallel is called the superconducting spin valve effect. We have prepared both types of spin valves by growing Fe/V thin-film heterostructures with epitaxial quality on MgO͑001͒ substrates. In the S/F1/N/F2-type spin valves the ferromagnetic layers were the first two Fe layers of a ͓Fe/V͔ superlattice coupled antiferromagnetically via the interlayer exchange interaction. Here we observed a superconducting spin valve shift of up to ⌬T S Ϸ 200 mK when aligning the sublattice magnetization in an external magnetic field. In the F1/S/F2-type spin valves the ferromagnetic layer F1 was either a ͓Fe/V͔ or a ͓Fe x V 1−x / V͔ superlattice, the F2 layer was a Fe-, a Co-, or a Fe x V 1−x film. Using weakly ferromagnetic Fe x V 1−x alloy layers as F1 and F2 we find a spin valve effect of up to ⌬T S Ϸ 20 mK, which is more than a factor of 2 larger than reported in the literature before for spin valves with comparable transition temperatures. Our results indicate that a high interface transparency and a large superconducting correlation length are prerequisites for the observation of a sizable superconducting spin valve effect.