Isotactic polypropylene-block-polyethylene block copolymers (iPP-b-PE) composed of crystalline blocks of isotactic polypropylene (iPP) and linear polyethylene (PE) of different block lengths have been synthesized with a living and stereoselective pyridylamidohafnium catalyst. The structure and morphology of iPP-b-PE that develop upon crystallization from the melt are presented. Temperature and time resolved X-ray diffraction experiments in wide (WAXS) and small angles (SAXS) recorded during cooling from the melt indicate that PE blocks crystallize first upon cooling and the iPP block crystallizes at lower temperatures and nucleates over the crystals of PE formed before. The SAXS data indicate that PE lamellar stacks formed first at high temperature have higher periodicity of 30 nm, whereas iPP lamellar stacks formed after at lower temperature have lower periodicity of 11–12 nm. The crystallization of the iPP and PE blocks drives microphase separation and determines the final morphology leading to a lamellar morphology characterized by alternation of amorphous and crystalline layers. At nanoscale the morphology is characterized by alternating iPP and PE microdomains, each domain including stacks of lamellar crystals of iPP or PE of different periodicities, separated by the corresponding amorphous regions of iPP or PE. Polarized optical micrographs of the melt-crystallized samples show the presence of bundle-like crystals in samples with longer block of iPP and of small banded spherulites in samples with longer block of PE. The observation of banded spherulites typical of PE suggests that the crystallization of PE defines the global morphology and is not altered by the structure of the melt, confirming that crystallization of PE occurs first upon cooling from the melt.