And with the victory, they kept Netherlands from becoming the first nation to win three consecutive women's field hockey gold medals.
Great Britain's goalkeeper Maddie Hinch saves a penalty from Netherland's Maartje Paumen during the gold medal match at the Rio Olympic Games.
Great Britain has won an Olympic gold after a nail-biting women's final against the Netherlands.
Great Britain celebrate the gold medal in the women's hockey at the Rio Olympics Games. "You can be the villain, but you can also be the hero for the moment". That was a huge team effort.
And they emulated that achievement by clinching gold on penalty strokes following a 3-3 draw with the mighty Dutch. I've had a really rollercoaster 24 hours, I've been a bit sick and I just did not know how I was going to be feeling today.
Hannah Macleod described the feeling of becoming an Olympic champion as "every bit as unbelievable as I'd ever hoped".
Hinch is a great believer in homework. "It was quite helpful that the Dutch had a shootout [against Germany] a day before".
"It helped that the Dutch had a shoot-out in their semi-final, so that gave me a chance to see what they do, but I basically give myself a game plan for each player and I execute that and thankfully it worked". It is all in the notebook.
"Over the years - I am constantly keeping my database up to date". I never thought we were going to win or they were going to win. "I retire as Olympic champion so it's a good way to go out", she said.
"What's sport without some drama, so on to the next one for me".
The 27-year-old from West Sussex said: "I just stayed in the moment. We've done this whole process together, we train together, we live together but it's not an excuse not to sprint for the bronze medal".
Holland, who beat her flatmate Non Stanford to make into onto the podium, said: "I can't describe it right now".
Helen Richardson-Walsh scored from a penalty stroke and Hollie Webb sealed the win with her penalty.
Helen and Kate Richardson-Walsh married in 2013 and, when asked what it meant to win Olympic gold alongside her wife, 34-year-old Helen said: 'It's pretty special. "To do it with your wife standing next to ...we will cherish this for the rest of our lives".
In the shoot-out, both sides missed their first two attempts but Britain grabbed the lead when Bray was fouled as she took her turn.
"I was so confident. I know how that inspires her, the passion of wanting to prove others wrong and deliver".
"What a journey it's been", added Helen.
"Seventeen years of many ups and downs, well majority downs probably", she reflected. "Shame it's silver", she added, gesturing to the medal which will join the two gold ones she already has at home. It's not been easy. The determination of Kerry's side ensured there were no more goals and it was time for a shootout. The pair will move to Holland to play for Bloemendaal next season. "I hope they are kind to us!" said Kate.
"We've genuinely been in this little bubble of our own routines".