She attended the University of California Los Angeles (UCLA), and graduated there in 1994. She was a four-year letter-winner in both basketball and volleyball, and is the first woman to earn All-America honors in both basketball and volleyball in the same year. She also led UCLA to NCAA volleyball titles in 1990 and 1991.
Williams was invited to be a member of the Jones Cup team representing the USA in 1996. She helped the team to a 9–0 record, and the gold medal in the event. Williams averaged 9.1 points per game. She also recorded 7.0 rebounds per game, highest on the team.
Williams was named to the USA national team in 1998. The national team traveled to Berlin, Germany in July and August 1998 for the FIBA World Championships. The USA team won a close opening game against Japan 95–89, then won their next six games easily. In the semifinal game against Brazil, the USA team was behind as much as ten points in the first half, but the USA went on to win 93–79. The gold medal game was a rematch against Russia. In the first game, the USA team dominated almost from the beginning, but in the rematch, the team from Russia took the early lead and led much of the way. With under two minutes remaining, the USA was down by two points but the USA responded, then held on to win the gold medal 71–65. Williams averaged 12.3 points per game, second highest on the team, and averaged 9.6 rebounds per game, highest on the team.
After the ABL folded, she was selected by her hometown team, the Utah Starzz in the first round (third pick overall) of the 1999 WNBA Draft on May 4, 1999.
Williams won an Olympic Gold Medal as a member of the U.S. women's basketball team during the 2000 Summer Olympics in Sydney, Australia.
In 2002, she opened a restaurant called Natalie's in Salt Lake City, Utah. She carried the Olympic Torch in the Salt Lake City area prior to the 2002 Winter Olympics. She also was named to the United States 2002 World Championship Games team.
She played with the Starzz from 1999 to 2002. However, just a few weeks prior to the start of the 2003 season, she was traded to the Indiana Fever in a multi-player deal on May 1, 2003.
Prior to the start of the 2005 season, Williams announced that she would retire after the season ended, saying that she will concentrate on raising her adopted twins, as well as serving as an assistant coach for Skyline' high school Girls basketball team in Salt Lake City, Utah, and launching a new career in the real estate Business. She is remembered by fans as one of the best rebounding power forward in the early history of the WNBA.