A set of integers is called sum-free if it contains no triple (x, y, z) of not necessarily distinct elements with x+y = z. In this paper, we provide a structural characterisation of sum-free subsets of {1, 2, . . . , n} of density at least 2/5 − c, where c is an absolute positive constant. As an application, we derive a stability version of Hu's Theorem [Proc. Amer. Math. Soc. 80 (1980), 711-712] about the maximum size of a union of two sum-free sets in {1, 2, . . . , n}. We then use this result to show that the number of subsets of {1, 2, . . . , n} which can be partitioned into two sum-free sets is Θ(2 4n/5 ), confirming a conjecture of Hancock, Staden and Treglown [arXiv:1701.04754].