In this paper, Lorentz boosts and Wigner rotations are considered from a (complexified) quaternionic point of view. It is demonstrated that, for a suitably defined self-adjoint complex quaternionic 4-velocity, pure Lorentz boosts can be phrased in terms of the quaternion square root of the relative 4-velocity connecting the two inertial frames. Straightforward computations then lead to quite explicit and relatively simple algebraic formulae for the composition of 4-velocities and the Wigner angle. The Wigner rotation is subsequently related to the generic non-associativity of the composition of three 4-velocities, and a necessary and sufficient condition is developed for the associativity to hold. Finally, the authors relate the composition of 4-velocities to a specific implementation of the Baker–Campbell–Hausdorff theorem. As compared to ordinary 4×4 Lorentz transformations, the use of self-adjoint complexified quaternions leads, from a computational view, to storage savings and more rapid computations, and from a pedagogical view to to relatively simple and explicit formulae.