Late qualifier Nicola Wilson will be the first of the Team GB eventing team to compete after the order was announced on Friday.
Wilson will be followed by Mary King, Zara Phillips, and Tina Cook, with world number one William Fox-Pitt on the final stage of the team pursuit.
The riders walked around all 28 fences of the six-kilometre cross-country course for the first time yesterday, a route that will challenge the world's best riders over at Greenwich Park.
Speaking at the park, Team Leader Will Connell praised the Olympic venue: “It’s truly a great venue and one that will go down in history and be remembered for many years.
“The cable cam running across the park will give us some shots of equestrian sport that are going to be truly memorable. I know the park has had its critics but I believe the venue will put our sport right up there.”
Contesting his fourth Olympic Games, Fox-Pitt also praised the venue. And in the only sport on the Olympic programme that men and women compete together on equal terms, he joked about being the only male on his team.
The world number one said: “The girls keep me in order and look after me, I feel very lucky. Who else can say they’re in a team of four beautiful blondes, I’m rather enjoying it.
“We feel incredibly lucky to be here. It’s very exciting to be in the Olympic Village and to be part of the British team, and not just the British equestrian team. To have the venue in London will bring equestrian to a wider audience and particularly to the east end of London and let’s hope a lot of people will enjoy it.”
Ahead of tonight’s Opening Ceremony, Connell announced that his team would not be attending the event as they focus on their performance.
He said: “Team GB is here with a very professional body of athletes and the primary reason for coming to an Olympics is to deliver your personal bests. I’ve heard the Opening Ceremony is amazing, but the athletes have made the decision that they are putting competition first and they won’t be going.
“I hope that they return with medals round their necks to enjoy the Closing Ceremony.”