A convenient protocol for stereodivergent hydrogenation of alkynes to E‐ and Z‐alkenes by using nickel catalysts was developed. Simple Ni(NO3)2⋅6 H2O as a catalyst precursor formed active nanoparticles, which were effective for the semihydrogenation of several alkynes with high selectivity for the Z‐alkene (Z/E >99:1). Upon addition of specific multidentate ligands (triphos, tetraphos), the resulting molecular catalysts were highly selective for the E‐alkene products (E/Z >99:1). Mechanistic studies revealed that the Z‐alkene‐selective catalyst was heterogeneous whereas the E‐alkene‐selective catalyst was homogeneous. In the latter case, the alkyne was first hydrogenated to a Z‐alkene, which was subsequently isomerized to the E‐alkene. This proposal was supported by density functional theory calculations. This synthetic methodology was shown to be generally applicable in >40 examples and scalable to multigram‐scale experiments.