The 37-year-old arrived at Smart Works, based in St Charles Hospital in north Kensington, west London, at 11am - just hours after it was announced she was to become a patron of the charity.
The new charity helps long-term unemployed and vulnerable women get back into work.
Pregnant Meghan, due to give birth in spring, arrived wearing a Hatch dress and an Oscar de la Renta coat for the visit. Hatch is a maternity brand.
She was met by chief executive Kate Stephens and waved at the gathered press before entering the hospital.
At the charity headquarters this morning Meghan spoke with Ms Stephens, Chair Lady Juliet Hughes-Halley, dressing volunteer Louise Warner, interview coach Marina Novis and two former clients Sarah Barrett and Ashwak Dadey who both benefited from Smart Works.
The Duchess helped to pick out an outfit for Patsy Wardally, 56, opting for a lovely brown coat.
During a chat with staff and volunteers Meghan said: "It's not just donating your clothes and seeing where they land. It's being part of each others' success stories as women.
"It's not hand me downs, it's saying 'okay, this is the blazer I wore that helped me with that interview and I want this to be the piece that helps a woman have that part of her story'.
"To know as a woman coming in, I would imagine, that you have so many other women believing in you is the piece which makes it so special."