A variety of ZnSe nanostructures, including the single-, bi- and tri-crystal nanobelts, are successfully fabricated through the thermal evaporation method and comprehensively investigated by a combination of various transmission electron microscopy (TEM) techniques. All nanostructures are of metastable wurtzite phase and the bi- and tri-crystal nanobelts are both mediated by the {013} twinning, with the single crystal nanobelts as building blocks. Benefiting from the commonly observed morphological evolutions, not only the crystallographic relations for different variants in an individual bi- or tri-crystal nanobelt, but also the intrinsic connections between different morphologies are fully understood by selected area electron diffraction, convergent beam electron diffraction and high-resolution TEM techniques, which reveals that the accompanying formation of tri-crystal nanobelt, the {013} relationship, though maintained still, is not as strict as that in a bi-crystal nanobelt and holds a ∼0.75° deviation for a case study; the angles between adjacent twinning variants/planes are compressed from ∼125.0° in bi-crystal nanobelts to ∼120°, and finally form an asymmetric twinning plane distributions. The study helps deepen the understanding of tri-crystal and related complex semiconductor nanostructures.