To specify a grain boundary at a macroscopic length scale requires the specification of five degrees of freedom. We use a specification in which three degrees of freedom associated with the boundary misorientation are in an orthogonal subspace from two associated with the mean boundary plane. By using Rodrigues vectors to describe rotations, we show how paths through these subspaces may be characterized. Some of these paths correspond to physical processes involving grain boundaries during microstructural evolution. Exploiting the orthogonality of the subspaces, a metric to measure ‘distance’ between two boundaries is defined in terms of the minimum set of rotations required to map one boundary on to the other. We compare our metric with others that have appeared. The existence of rotational symmetry in face-centred cubic crystals leads to as many as 2304 equivalent specifications of a boundary. We illustrate this multiplicity of descriptions for the (111) twin and a more general boundary. We present an algorithm to evaluate the geodesic distance between two boundaries, and apply it to identify the path along which the distance between these two boundaries is minimized. In general, the shortest path does not involve descriptions of boundary misorientations with the smallest misorientation angles.