AbstractThe copper‐rich intermetallics CaCu9Cd2 and EuCu9Cd2 were synthesized from the elements in sealed tantalum tubes in a high‐frequency furnace. Both compounds were characterized by X‐ray powder and single crystal diffraction: Ce(Mn0.55Ni0.45)11 type, P4/mbm, a = 844.2(1), c = 504.72(8) pm, wR2 = 0.0216, 345 F2 values, 23 variables for CaCu9Cd2 and a = 844.1(2), c = 505.5(1) pm, wR2 = 0.0200, 331 F2 values, 24 variables for EuCu9.14Cd1.86. The europium‐based crystal showed a small mixed Cu/Cd occupancy on the 4g site. The calcium (europium) atoms have the high coordination number 20 (16Cu + 4Cd). These polyhedra are condensed via common Cu4 squares along the c axis. Other striking structural motifs are segregated Cd2 pairs (291 pm in CaCu9Cd2) in copper coordination and slightly distorted Cu2@Cu8Cd4 icosahedra. The latter are connected via common Cd2 pairs along c and form the motif of tetragonal rod packing. EuCu9Cd2 shows paramagnetic behavior above 100 K with an experimental magnetic moment of 7.82(1) μB/Eu atom, indicating purely divalent europium.