The twelve teams in the tournament were divided into two groups of six, with each team initially playing round-robin games within their group. Following the completion of the round-robin stage, the top four teams from each group advance to the quarter-finals. The two semi-final winners meet for the gold medal match, while the semi-final losers play in the bronze medal match.
Each of the Continental Champions from five confederations received an automatic berth. Brazil as the host nation qualified automatically but with a rider. Due to the standard of field hockey in Brazil, the International Hockey Federation (FIH) and the International Olympic Committee (IOC) required Brazil to place higher than thirtieth in the FIH World Rankings by the end of 2014 or finish no worse than sixth at the 2015 Pan American Games in order to qualify as host nation. They achieved this by beating the United States on a penalty shoot-out in the quarterfinal, ensuring a top four finish. In addition to the six highest placed teams at the Semifinals of the 2014–15 FIH Hockey World League not already qualified, the following twelve teams, shown with final pre-tournament rankings, will compete in this tournament.[5][6]
^South Africa won the continental qualifier however the team did not participate in the 2016 Olympics. South African Sports Confederation and Olympic Committee (SASCOC) and South African Hockey Association (SAHA) made an agreement on the Rio 2016 Olympics qualification criteria that the Continental Qualification route would not be considered.[7][8] As a result, New Zealand, as the highest-ranked team from the 2014-15 Hockey World League Semifinals not already qualified, participated instead.[9][10]
As per statistical convention in field hockey, matches decided in regular time are counted as wins and losses, while matches decided by penalty shoot-outs are counted as draws.