A rare precious metal binary citrate represented by palladium in the form of a water-rich Na–Pd intermetallic aggregate has been isolated and crystallographically characterised. It shows a penta-anionic [NaPd3(citrate)3]5− core balanced by [Na3]3+ and Na+ hydrates in a 3-D coordination network stabilised exclusively by citrate bridges and fortified by extensive H-bonding.