This work introduces a new concept, the so-called Darboux family, which is employed to determine coboundary Lie bialgebras on real four-dimensional, indecomposable Lie algebras, as well as geometrically analysying, and classifying them up to Lie algebra automorphisms, in a relatively easy manner. The Darboux family notion can be considered as a generalisation of the Darboux polynomial for a vector field. The classification of r-matrices and solutions to classical Yang–Baxter equations for real four-dimensional indecomposable Lie algebras is also given in detail. Our methods can further be applied to general, even higher-dimensional, Lie algebras. As a byproduct, a method to obtain matrix representations of certain Lie algebras with a non-trivial center is developed.