An efficient enantioselective synthesis of vicinal amino alcohols by C−H functionalization of pyrazolo-substituted arenes and O-allyl hydroxylamines as amino alcohol C3-synthon with built-in amidation capability is reported. The transformation is enabled by a chiral cyclopentadienyl cobalt(III) complex, providing enantioselectivities of up to 98:2 er with a broad range of substrates. The generated chiral β-amino alcohols are versatile building blocks of high synthetic value. Notably, turnover numbers of up to 52 were achieved ranging in the very top-end for asymmetric high-valent cobalt C−H functionalization catalysis.