"I personally met with them and they all have their lifesavings on the line and a couple of these guys were out of work," Rancic said.
Of the Dairy Poop founders, who are related, two were unemployed because they had gotten laid off.
"They're just heartwarming stories. It makes you want to root for each and every one of them," he said.
Another contestant, Locally Laid Egg Company, from Duluth, Minn., is a pasture-raised egg company with about 2,500 chickens. With hens all named Lola, the founder feeds his chickens locally-sourced corn on a pasture for healthier chickens.
Barley Labs, based in Durham, N.C., is named after the founding couple's rescue dog, a black lab. They started making dog treats out of their home with grain from a local brewery and turn it into dog treats.
Rancic admiringly describes more of the contestants' "compelling" stories, including the Barley Labs co-founder Teresa Chu quitting her job to start to create treats out of their kitchen.
With three flavors (peanut butter, pumpkin and cheese), the company donates 10 cents from every bag to an animal shelter.
As the first winner of NBC's "The Apprentice," Rancic nine years ago was in a similar position as the co-founders of Barley Labs and the other contestants.
"For me, it's come full circle," he said. "Ten years ago, I got the opportunity of a lifetime when Trump hired me on, got to win that show and work on that project, now I get to do it for someone else."