After qualifying for the 2016 Rio Olympics in Japan, the Matildas faced Canada in their first group stage match with Williams in goal. The team tied their next group stage match against Germany 2–2. After defeating Zimbabwe 6–1, the team finished third in Group F and top ranking in the third place teams advancing to the knockout stage. During their "thrilling" quarterfinal match against Brazil, Williams was put to the test in a penalty shootout after a 0–0 draw. Despite saving a penalty from Marta, the Matildas were ultimately edged out 7–6 during the shootout and knocked out of the competition.