Nucleation eventsa nd crystal growth can be guided by molecular recognition at interfaces through intermolecular interactions. The short-acting antimicrobial sulfa drug sulfathiazole is knownf or its concomitant crystallization, which has five knownp olymorphs, due to conformational flexibility and hydrogen-bond synthon variation. In its development stage of ad rug the issue of concomitant crystallization needs to be addressed with respect to patent litigation, including legal actions to protectp atentsa gainst in-fringement.Afunctional self-assembled monolayer (SAM) of organict hiol on ag old surface has been employed as an efficient approacht oc ontrol concomitant nucleation of such flexible drugs. The crystallization on aS AM surface is mostly kinetically driven and often leads to the nucleation of novel metastable forms. Spectroscopic, thermala nalysis and X-ray diffraction studies reveal that ap reviously unknown, sixth form of the drug nucleates on the designedS AM surface.[a] P.