The 29-year-old was all smiles as she was seen filming scenes with her co-star Molly Bernard.
The blonde beauty wore a black leather mini dress that featured a slit up her thigh.
She added a large monochrome knitted cardigan and black leather gloves to complete her daredevil look.
The former Lizzy McGuire star accessorized with a thick light coloured choker necklace and dainty stud earrings.
Her make-up was a little more dramatic than usual as she opted to wear mauve lipstick and heavy black eye make-up.
The duo were currently filming scenes for Season 4 of the show, which stars Sutton Foster as a 40-year-old woman who pretends to be 26 in order to get a job in the highly competitive world of publishing – and succeeds.
Season 3 found Liza (Foster) working under Diana (Miriam Shor) as she tried to figure out how to balance her real life and her fake life.
She is best friends with Maggie (Debi Mazar) in reality but her younger crew of friends includes co-workers Kelsey (Duff) and fashion publicist Lauren (Bernard).
Ben Rappaport and India de Beaufort are among those joining the Season 4 cast, alongside other season regulars Nico Tortorella and Peter Hermann.
The 12-episode fourth season was ordered ahead of the show’s Season 3 premiere last year.
Meanwhile, Duff has had to deal with an uncomfortable situation with her ex Mike Comrie.
TMZ reported last month that police were investigating the former Pittsburgh Penguin for an alleged rape, though he claims the sex in question - which occurred at his home - was consensual.
He was scheduled to submit DNA to police recently in connection with the case, as DailyMail.com revealed exclusively nearly two weeks ago.
The Younger actress was married to the now-retired hockey player from 2010 until last year, and their son Luca was born in 2012.
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