She was joined on the shoot by four British blokes; two musicians and two models – one of whom just happened to be her younger brother Alex.
The 17-year-old was signed up to help showcase pieces alongside his big sister from three of the label's fashion brands – Burberry Prorsum, Burberry London and Burberry Brit - shot by famed photographer Mario Testino.
He was also photographed alongside Matt Gilmour, son of Pink Floyd's Dave Gilmour, Max Hurd, the grandson of the former Foreign Secretary, Lord Douglas Hurd and George Craig, the front man of indie band One Night Only.
It was the first modelling assignment for Alex, who briefly appeared as an extra in Harry Potter and the Order of the Phoenix, although he is now signed up to famed agency, Storm.
Having her sibling on the set meant a great deal to Emma who admitted during the shoot: "Today is really special for me in a number of different ways."
As well as expressing happiness at reuniting with Mario and Burberry's creative director - and current British designer of the year, Christopher Bailey - the 19-year-old added: "They also shot my brother in the campaign. He's having a great time. He's so psyched."
It's the second time that Emma – currently reading literature at the prestigious Brown University in Rhode Island – has been snapped for Burberry, following her debut in June.
The starlet, who is quickly earning a name for herself in the world of fashion, has also been photographed by Chanel legend Karl Lagerfeld for a special spread in a French magazine.