The veteran singer was honoured in the Queen's New Year Honours list for his services to music.
Penny, 36, wore a £700 Dolce and Gabbana chiffon leopard-print dress teamed with £370 Jimmy Choo shoes.
The crinkly rocker, 62, sported a tie with a skull and swords motif, navy blazer, white Ralph Lauren trousers and stripy shirt.
Prince Charles presented the award.
'It's a marvellous occasion. We're the only country in the world to honour the common man,' said Rod.
