The actress made the confession during a recent joint interview with the legendary star for Fox News, and the news took De Niro by surprise.
She said, "That was when I very first met you. Did I ever tell you that? It was my very first interview ever... never thinking I would get the part, which of course I didn't. I had always dreamed of working with him, and so I was just very excited (to land a role in The Family)."
After hearing the secret, a stunned De Niro replied, "Really? Oh, wow."
Pfeiffer had previously appeared with De Niro in 2007 fantasy Stardust and 2011 ensemble romantic comedy New Year's Eve, but they had never been in the same scenes until Luc Besson brought them together to portray husband and wife in The Family.