We investigate the decays of the excited (bqover ¯) mesons as probes of the short-distance structure of the weak ΔB=1 transitions. These states are unstable under the electromagnetic or strong interactions, although their widths are typically suppressed by phase space. Compared to the pseudoscalar B meson, the purely leptonic decays of the vector B^{*} are not chirally suppressed and are sensitive to different combinations of the underlying weak effective operators. An interesting example is B_{s}^{*}→ℓ^{+}ℓ^{-}, which has a rate that can be accurately predicted in the standard model. The branching fraction is B∼10^{-11}, irrespective of the lepton flavor and where the main uncertainty stems from the unmeasured and theoretically not well known B_{s}^{*} width. We discuss the prospects for producing this decay mode at the LHC and explore the possibility of measuring the B_{s}^{*}→ℓℓ amplitude, instead, through scattering experiments at the B_{s}^{*} resonance peak.