Charged kaon–deuteron interactions offer a sensitive probe of the strangeness sector of QCD at low energy, particularly through their scattering parameters. Despite available theoretical predictions, experimental constraints remain absent, particularly for the K− d system. The first measurement of femtoscopic correlation functions for K− d ⊕ K+ d and K+ d ⊕ K− d particle pairs in Pb–Pb collisions √ at sNN = 5.02 TeV recorded by ALICE at the LHC is presented. Correlation functions for both systems are analyzed in three centrality classes and fitted using the Lednický–Lyuboshitz model to extract the source size and strong interaction scattering lengths. The K− d scattering length is found to +0.21 be ℜ f0 = −1.44 ± 0.15 (stat.)+0.10 −0.10 (syst.) fm and ℑ f 0 = 1.34 ± 0.33 (stat.)−0.15 (syst.) fm, while for +0.09 + K d the value ℜ f0 = −0.68 ± 0.16 (stat.)−0.09 (syst.) fm is obtained. These results provide the first constraints on the K± d interaction modeling at low energy, delivering a long-awaited experimental benchmark for testing chiral QCD dynamics.