"There have been a lot of awkward ones," the E! co-host recalled during an appearance on Watch What Happens Live!. "Oh, I know… duh! Russell Crowe," she exclaimed. "(He) was so mean to me!"
"I had been at E! for a year, and I was literally like, 'I'm gonna go easy because he's pretty tough'," she said of the sometimes-prickly Oscar winner. "And so I said, 'Are you excited to be here tonight? Your big movie premiere…'
"And he goes, 'I'm contractually obligated to be here. What's your next question?'"
Giuliana, 38, continued, "And I go, 'Ok, so isn't it wonderful to see all your fans?' And he goes, 'That's your second question?' And then he goes, 'One, two, you're through' and walked away."
In contrast, Giuliana's most successful interview is the one with her future husband Bill Rancic. The Celebrity Apprentice winner later asked Giuliana out in the parking lot, and they ended up tying the knot in 2007.
Bill, 42, has said it was love at first sight. "When we first met, I think we knew there was something special. On our second date — this is what we tell people — we were making plans for six or seven months in advance, which I had never done in my life before.
The couple have overcome some tremendous hurdles together. In 2011, Giuliana was diagnosed with breast cancer, which she bravely battled with her husband by her side.
"Bill was everything," she has said. "My husband was everything throughout the process — from getting diagnosed 'til today. And I don't know how I would have done it without him, I really don't."
They also faced a long journey to parenthood, which was documented in their reality show Giuliana and Bill.
After several failed attempts at IVF, they welcomed a son together via surrogate and are now proud parents to 19-month-old son Duke.
The couple hope to expand their family further, and were seen asking their surrogate is she would be willing to carry their second child during the season finale of their show last year.
"We're always talking about baby number two and we would love to expand our family," Giuliana told US Weekly. "We don't know, because of everything we've been through, if the next one will have to be the last one.
"In that case, I would love a girl as well, because I have my boy and I adore him, and it would be nice to have a little girl and teach her all my crazy ways!
"But part of me feels like if we're only going to have two that it would be nice for him to have a brother — then they'd be close in age and they can pal around. That would be kind of cool too."