The Krein–von Neumann extension is studied for Schrödinger operators on metric graphs. Among other things, its vertex conditions are expressed explicitly, and its relation to other self-adjoint vertex conditions (e.g. continuity-Kirchhoff) is explored. A variational characterisation for its positive eigenvalues is obtained. Based on this, the behaviour of its eigenvalues under perturbations of the metric graph is investigated, and so-called surgery principles are established. Moreover, isoperimetric eigenvalue inequalities are obtained.