The Black Sticks men will play Australia on the opening day of the Olympic hockey competition while the New Zealand women will play Korea a day later.
The International Hockey Federation (FIH) has released the draw for the Rio games.
Running from August 7-20 at Deodoro Olympic Park, the events will feature the 12 men's and 12 women's hockey teams who qualified through the Hockey World League and Continental Championships.
The New Zealand men are in action against trans-Tasman rivals Australia at 4:30am on Sunday 7th August (NZ time) before the women open their campaign against Korea at 1:00am Monday morning.
Two pitches will host both events and for the first time in an Olympic hockey competition, quarter-finals will be played with the top four teams from each pool qualifying for the knock-out stages.
The winners of the quarter-finals will qualify for the semi-finals which will determine who will play in the gold and bronze medal matches.
The men's medal matches are scheduled for Friday 19th August and the women's the following day, on Saturday 20th August.
Hockey New Zealand High Performance Manager Terry Evans said both teams were looking forward to the challenge of some exciting match-ups in their hunt to win a medal.
"There are no easy games at the Olympics and you can certainly see that in the draw for Rio which showcases the best of the best," Evans said.
"The men go up against world number one Australia in their first match so that will be an exciting challenge and a tough test to set the tone.
"We are confident that both our men and women have the talent within their squads right now to really make a mark and achieve some great results in Rio."
The New Zealand men's and women's hockey teams will be named in June by the New Zealand Olympic Committee.
The hockey competition at the Rio 2016 Olympic Games comprises women's and men's events, with the same format and rules for both.
In the preliminary round 12 teams are divided into two pools of six teams.
Each team plays every other team in its pool.
The top four teams in each pool proceed to the quarter-finals, with the remaining four teams eliminated at this stage.
The winners of the quarter-finals progress to the semi-finals, the winners of which meet in the gold medal match.
The losers of the semi-finals will play for the bronze medal.