4′-epidaunorubicin hydrochloride is provided in a crystalline form which is stable and readily soluble. A process of producing the crystalline form includes crystallizing 4′-epidaunorubicin hydrochloride in a solvent system including (a) solvent A selected from C1 and C2 halogenated solvents and mixtures thereof, (b) solvent B selected from C1-C5 straight and branched alcohols and mixtures thereof, and (c) solvent C selected from C1-C5 straight and branched alcohols and mixtures thereof, wherein solvent C is selected to provide lower solubility to 4′-epidaunorubicin hydrochloride than solvent B. A method of producing an anthracycline using crystalline 4′-epidaunorubicin hydrochloride is also provided.