On 27 February 2010, Kowalczyk beat Norway's Marit Bjørgen by 0.3 seconds to win the gold medal in the women's 30 km classical event in the 2010 Winter Olympics. She posted a time of one hour, 30 minutes, 33.7 seconds. She earned two more medals in Vancouver, taking silver behind Bjørgen in the individual sprint classic on 17 February 2010, and bronze in the 15 km pursuit on 19 February 2010.
Kowalczyk criticized Marit Bjørgen and other competitors during the Olympic Games in 2010 for using anti-asthma drugs. Bjørgen won five medals in the Olympics, three of them gold. The drug is allowed by FIS if prescribed by an Olympic team physician. Kowalczyk later apologized for the timing of her statements, since the Games were still going on at the time. The asthma medication Marit Bjørgen is using, Symbicort, has since been removed from WADA's list of banned substances.