The 44-year-old British actor got married to Jolie, 41, in March 1996 after they met and fell in love on the set of 1995 movie "Hackers". The two separated just 18 months later and got divorced in February 1999.
Although it did not work out for them as a married couple, Lee Miller said he and the actress have remained pals and still speak.
When asked if he is still in touch with Jolie, he said, "Yeah, we're still friends."
"There wasn't one (a big deal), because we were both completely unknown. Angie wasn't ... It was pre all that."
After her split from Lee Miller, Jolie tied the knot with Billy Bob Thornton in 2000. They separated in June 2002 and divorced the following year.
Jolie then started dating her "Mr & Mrs Smith" co-star Brad Pitt, with whom she got married in 2014. They too parted ways last year.