We study T-duality chains of five-branes in heterotic supergravity where the first order α ′ -corrections are present. By performing the α ′ -corrected T-duality transformations of the heterotic NS5-brane solutions, we obtain the KK5-brane and the exotic 5 2 2 -brane solutions associated with the symmetric, the neutral and the gauge NS5-branes. We find that the Yang-Mills gauge field in these solutions satisfies the self-duality condition in the three-and two-dimensional transverse spaces to the brane world-volumes. The O(2, 2) monodromy structures of the 5 2 2 -brane solutions are investigated by the α ′ -corrected generalized metric. Our analysis shows that the symmetric 5 2 2 -brane solution, which satisfies the standard embedding condition, is a T-fold and it exhibits the non-geometric nature. We also find that the neutral 5 2 2 -brane solution is a T-fold at least at O(α ′ ). On the other hand, the gauge 5 2 2 -brane solution is not a T-fold but show unusual structures of space-time.