We present the first calculation for the hadroproduction of a W boson in association with a massive bottom (b) quark-antiquark pair at next-to-next-to-leading order (NNLO) in QCD perturbation theory. We exploit the hierarchy between the b-quark mass and the characteristic energy scale of the process to obtain a reliable analytic expression for the two-loop virtual amplitude with three massive legs, starting from the corresponding result available for massless b quarks. The use of massive b quarks avoids the ambiguities associated with the correct flavor assignment in massless calculations, paving the way to a more realistic comparison with experimental data. We present phenomenological results considering proton-proton collisions at center-of-mass energy √s = 13.6  TeV for inclusive Wb¯b production and within a fiducial region relevant for the associated production of a W boson and a Higgs boson decaying into a b¯b pair, for which Wb¯b production represents one of the most relevant backgrounds. We find that the NNLO corrections are substantial and that their inclusion is mandatory to obtain reliable predictions.