The classification of Willmore 2-spheres in the n-dimensional sphere S n is a long-standing problem, solved only when n = 3, 4 by Bryant, Ejiri, Musso and Montiel independently. In this paper we give a classification when n = 5. There are three types of such surfaces up to Möbius transformations: (1) super-conformal surfaces in S 4 ; (2) minimal surfaces in R 5 ; (3) adjoint transforms of super-conformal minimal surfaces in R 5 . In particular, Willmore surfaces in the third class are not S-Willmore (i.e., without a dual Willmore surface).To show the existence of Willmore 2-spheres in S 5 of type (3), we describe all adjoint transforms of a super-conformal minimal surfaces in R n and provide some explicit criterions on the immersion property. As an application, we obtain new immersed Willmore 2-spheres in S 5 and S 6 , which are not S-Willmore.