Summary: From kinetic theory we have rigorously derived singularity‐free Brownian dynamics analyses of nanoparticle rotational dynamics. The rigid non‐spherical nanoparticles incorporate all three rotational degrees of freedom. This was achieved by using the components of Cartesian rotation vectors as the generalized coordinates describing angular orientation. The new results constitute an important advance compared to the situation when Eulerian angles specify angular orientation. Our finding eliminates one of the main longstanding obstacles to detailed studies of nanoparticle rotational dynamics in the diffusion time domain. The described formalism is applicable to a wide range of nanoparticle systems including liquid crystals, biopolymers, and colloids.