After qualifying for the 2016 Rio Olympics in Japan, the Matildas faced Canada in their first group stage match and lost 2–0 with Catley subbing in for Sam Kerr at halftime. 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, the defense kept Brazil to a 0–0 draw, but the Matildas were ultimately edged out 7–6 during the shootout and knocked out of the competition. Catley competed in all four games for the Matildas making three starts.