Microstructure evolution in the commercial Mg-Nd-Gd-Zn-Zr alloy Elektron 21, solidified under nearly isothermal conditions, has been studied via in-situ X-ray radiography. For cooling rates T ≤ 0.075 K/s, primary equiaxed α-Mg dendrites undergo a morphological transition after nucleation and an initial stage of growth. The growth regime is observed to change abruptly from a 3D to a more pronounced anisotropic sheet-like growth occurring predominantly along 〈112 ̅ 0〉 direction, with a 4-5 times increase in the growth velocity. The experimental results together with thermodynamic calculations and density functional theory simulations give support to relate the morphology transition to the formation of ordered rare earth-zinc dimers in the {0001} basal plane and {101 ̅ 1} pyramidal plane of α-Mg lattice. At the temperature where the morphological transition occurs, it is found that both the solute concentration and zinc diffusivity in α-Mg are high enough for dimer formation to occur 2 within a diffusive layer extending a few micrometres from the solid-liquid interface into α-Mg, and thereby open for increased solute-partitioning at the growth front.