(Riemannian geometry) Four is the only dimension $n$ in which the adjoint representation of SO($n$) is not irreducible. Since the adjoint representation is isomorphic to the representation on 2-forms, this means that the bundle of 2-forms on an oriented Riemannian manifold decomposes into self-dual and anti-self-dual forms. 2-forms are particularly significant, since the curvature of a connection is a 2-form. In particular the curvature of the Levi-Civita connection is a 2-form with values in the adjoint bundle, so it has a 4-way decomposition into self-dual and anti-self-dual pieces. Hence there are natural curvature conditions on Riemannian 4-manifolds which have no analogue in other dimensions (without imposing additional structure).
The impact of self-duality includes: special properties of Einstein metrics, Yang-Mills connections, and twistor theory for (anti-)self-dual Riemannian manifolds.