Nyong'o, who had won Best Supporting Actress a year earlier for her feature film debut in "12 Years a Slave", presented the Best Supporting Actor Award at the 2015 Academy Awards - which Simmons won for his powerful performance.
But things didn't go exactly to plan as, speaking on Marc Maron's "WTF" podcast, he opened up about the awkward moment while collecting the accolade.
"There's a billion people watching, and you're in the Kodak Theater with every famous actor you grew up watching, so I was a little nervous, and I never actually wrote an acceptance speech," he explained.
"I had a theme in mind… and I wanted to talk about what's most important in life, which is family," he said, adding he was "kind of formulating my thoughts" while he was walking up to the stage.
The star added, "Lupita Nyong'o was going to hand me the trophy and I reach out with one hand to take the trophy, and I reach out with the other hand to shake her hand, like we're two dudes making a business deal, and then I realised, 'Oh no, it's Hollywood. You're supposed to do the fake kiss on the cheek.' "
"So, I kind of awkwardly go in for the fake kiss on the cheek thing, and I gave her a little of a head butt. But (thankfully) not enough to take her down," the "21 Bridges" star recalled, admitting he was just glad "there wasn't a house laugh, because it was subtle enough that most people didn't notice."