Isotactic poly(1-butene) (i-PBu) is a polyolefin of industrial relevance which exhibits an interesting polymorphism. Upon cooling from the relaxed melt at atmospheric pressure, a tetragonal phase (Form II) develops. However, being metastable, this structure slowly evolves upon aging in the stable trigonal modification (Form I). Another trigonal modification, denoted Form I', can also crystallize directly from the melt if proper conditions are met, e.g., high pressure, low tacticity, ultrathin samples etc. In this work, we aim to verify whether, by acting on the nucleation stage via a proper thermal history, the direct formation of the trigonal polymorph from the melt in a bulk sample is possible. Nucleation of i-PBu has been tailored by means of the self-nucleation technique, imposed on previously aged samples (Form I). DSC and temperature-resolved WAXS show that different crystallization pathways can be observed, depending on the residual concentration of Form I self-nuclei. With decreasing self-nucleation temperature we first encounter "cross-nucleation" of the tetragonal crystal on trigonal nuclei, followed by concomitant crystallization of Form II and Form I' and eventually the sole formation of the trigonal modification (Form I'). (C) 2013 Elsevier Ltd. All rights reserved.