Motivated by the potential prospects of the B_c^∗ meson samples at hadron colliders, the bottom-changing B_c^∗ → ψ(1S,2S)P, η_c(1S,2S)P weak decays are first studied with the perturbative QCD approach, where P = π and K. It is found that branching ratio of the CKM-favored B_c^∗ → J/ψπ decay is about ∼ O(10^-8), which might be measurable at the future LHC experiments.