Summary: This article studies the Lie algebra \(\mathrm{Der}(\mathbf k\Gamma)\) of derivations on the path algebra \(\mathbf k\Gamma\) of a quiver \(\Gamma\) and the Lie algebra on the first Hochschild cohomology group \(HH^1(\mathbf k\Gamma)\). We relate these Lie algebras to the algebraic and combinatorial properties of the path algebra. Characterizations of derivations on a path algebra are obtained, leading to a canonical basis of \(\mathrm{Der}(\mathbf k\Gamma)\) and its Lie algebra properties. Special derivations are associated to the vertices, arrows and faces of a quiver, and the concepts of a connection matrix and boundary matrix are introduced to study the relations among these derivations, giving rise to an interpretation of Euler’s polyhedron formula in terms of derivations. By taking dimensions, this relation among spaces of derivations recovers Euler’s polyhedron formula. This relation also leads to a combinatorial construction of a canonical basis of the Lie algebra \(HH^1(\mathbf k\Gamma)\), together with a new semidirect sum decomposition of \(HH^1(\mathbf k\Gamma)\).