Lee made her Olympic debut aged nineteen at the 2004 Summer Olympics in Athens, joining the defending Olympic champion Yun Mi-jin and the 2001 World Champion Park Sung-hyun on the South Korean women's team. In the preliminary ranking round, which determined the seedings for the elimination rounds of the individual and team events, Lee, Park, and Yun broke the world record for the combined team score over 216 arrows, their total of 2,030 points from a maximum of 2,160 eclipsing the previous best set by the South Korean team at the 2000 Olympics. The score was nevertheless not classified as a new Olympic record because the ranking round took place prior to the opening ceremony. Lee's personal 72-arrow score additionally earned her the second seed for the women's individual event.
In the first round of elimination, she faced 63rd-ranked Lamia Bahnasawy of Egypt. Lee defeated Bahnasawy 164–127 in the 18-arrow match to advance to the round of 32. In that round, she faced 34th-ranked Greek archer Elpida Romantzi, defeating her 166–146. Lee then defeated 15th-ranked Margarita Galinovskaya of Russia 165–163, advancing to the quarterfinals.
In the quarterfinals, Lee faced Wu Hui-ju of Chinese Taipei, narrowly defeating the 10th-ranked archer 104–103 in the 12-arrow match. Lee advanced to the semifinals, where she defeated Yuan Shu-chi, also of Chinese Taipei, 104–98. This moved Lee to the gold medal match, pitting her against fellow Korean Park Sung-hyun. In the final 12-arrow match, Lee lost by two points to the 1st-ranked Park, finishing with a silver medal in women's individual archery while Park won the gold medal.

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