The 29-year-old star - who owns clothing and accessories brands Winter Kate and House of Harlow - will join model Elle Macpherson and singer-turned-designer Jessica Simpson on the TV show, which sees aspiring designers compete for a contract to have their prodcuts sold in retailers in the US.
The programme does not yet have an air date.
Just days ago, Nicole - who has children Harlow, three and 22-month-old Sparrow with rocker husband Joel Madden - announced she would be expanding her fashion range, with a new collection of handbags as part of her House of Harlow 1960 line.
Discussing her own design credentials, Nicole revealed she only ever created clothes she would want to wear herself.
She said: "My main goal for this particular collection - and for all the footwear that I design - is I want the shoes to look great but be comfortable at the same time.
"I'm a girl and I love shoes. Who doesn't want to make exactly what you want?"