We propose to utilize the exclusive Z-boson rare decays $Z\to \Upsilon \left(ns\right)+\gamma$ to constrain the $Zb\overline{b}$ couplings at the HL-LHC and 100 TeV proton-proton collider. We demonstrate that the event yield of the proposed processes is sensitive to the axial-vector component of the $Zb\overline{b}$ coupling and can provide complementary information to the jet-charge weighted single-spin asymmetry measurement at the EIC and the $gg\to Zh$ production rate measurement at the LHC. By applying the NRQCD factorization formalism, we calculate the partial decay width of $Z\to \Upsilon \left(ns\right)+\gamma$ to the NLO accuracy in strong interaction, which is found to agree with those obtained from the light-cone distribution amplitude approach. We show that the HL-LHC can break the degeneracy of the $Zb\overline{b}$ couplings, as implied by the precision electroweak data at LEP and SLC, if the signal efficiency can be improved by a factor of 1.7 from the present ATLAS analysis at the 13 TeV LHC with an integrated luminosity of $36.1{\mathrm{fb}}^{-1}$.