The low-temperature (LT) superstructure and the phase transition temperature have been investigated for a series of Cd6M crystalline approximants by transmission electron microscopy as well as electrical resistivity measurements. Except for M = Lu, Cd6M is found to undergo a phase transition to a monoclinic phase at a low temperature and the transition temperature (Tc) scales well with the size of the M atom. For M = Ca, Y, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er and Tm the LT superstructure is explained by a √2a × a × √2a lattice with the space group C2/c, and for M = Sr and Yb a √2a × 2a × √2a monoclinic lattice with P2/m. On the other hand, no phase transition is observed for M = Lu, indicating that a Cd4 tetrahedron at the cluster center remains disordered down to the lowest temperature, i.e. 16 K. It is shown that the volume inside the Cd20 dodecahedron plays a crucial role in the occurrence of the phase transition, and long-term aging in particular promotes the phase transition for late rare-earth elements such as Ho, Er and Tm, suggesting that the transition is sensitive to and is even hindered by disorder such as atomic vacancies. The absence of the transition for M = Lu is attributed to the highest activation energy for the transition due to the smallest volume inside the Cd20 dodecahedron.