Middleton, 33, and financier Matthews, 41, were en route to Rose Bay, where they boarded a sea plane to travel to Ku-ring-gai National Park for lunch.
While few details about their wedding have stayed secret - a guest tried to sell the reception menu featuring trout, lamb and cheesecake on eBay - Pippa Middleton and James Matthews have managed a coup by touching down in Sydney as part of their honeymoon.
Photos of them touching down have since been snapped up by publications in Britain. It was at Sydney Harbor that the two lovers were surprised by photographers on Wednesday when they were about to have lunch with some friends. Her new husband was casual in jeans and a blue pullover.
"[She] looked such a pro in her active wear", fellow Sydneysider Anna Frilingos told Fairfax Media, who also walked past them on her usual commute to work across the bridge. The summer-ready design is none other than Kate Spade New York's lantern poplin flounce dress which can be purchased for £335 and looks great with a pair of simple leather sandals.
As an active runner and cyclist, she regularly competes in fun runs and ultra marathon events for charity.
Pippa is the younger sister of Kate, the Duchess of Cambridge, who's married to Prince William.
The newlyweds have been holidaying since their May 20 nuptials.
After their lavish wedding the couple initially honeymooned at The Brando, a luxury resort on the private French Polynesian island of Tetiaro.
The pair have arrived in Sydney at just the right time.