The effect of supersaturation, nucleation temperature, cooling rate and solvent on the polymorphic crystallization of stavudine has been studied. Supersaturation is found to be the predominant controlling factor for the occurrence of polymorphs. When stavudine crystallizes from methanol or 2-propanol, form I nucleates preferentially at a low supersaturation level, whereas form II can be obtained at a high supersaturation level. When 1-butanol is used as solvent, apart from forms I and II, a newly found metastable form IV can crystallize out at a moderate supersaturation level. The relative stability of the above three polymorphs in decreasing order is: I > IV > II. In addition, the polymorphic transformation of stavudine in 2-propanol from form II to form I has been investigated by in situ Raman spectroscopy. The transformation rate is found to be accelerated significantly by increasing temperature and seeding with form I.