To prove the classical angular momentum commutation relation, the expression {Li, Lj} = εijkLk can be derived using the Levi-Civita symbol and the definition of the Poisson bracket. It is important to express Li in terms of the generalized coordinates qi and momenta pi. The discussion highlights that using square brackets can lead to confusion in classical mechanics. A participant expresses a desire to extend the relation to a general vector Vi, questioning how to construct such a vector while maintaining the relation {Vi, Lj} = εijkVk. The conversation emphasizes the need for clarity in notation and the proper formulation of vectors in classical mechanics.