Two Pd6 molecular aggregates (1 and 2), self-sorted via a template-free three-component self-assembly process, represent new examples of discrete architectures exhibiting very high proton conductivity [0.78 × 10(-3) S cm(-1) (1) and 0.22 × 10(-3) S cm(-1) (2)] at 300 K at low relative humidity (∼46%) with low activation energy comparable to that of currently used Nafion in fuel cells.