The Liverpool skipper racked up 114 caps for his country, scoring 21 times, and captained England in three major tournaments, the 2010 and 2014 FIFA World Cups and UEFA Euro 2012.
However, after failing to lead England out of Group D in Brazil, the 34-year-old has opted to bring the curtain down on his time on the national stage.
He told the Football Association's official website: "I have enjoyed every minute of representing my country and it is a sad day for me knowing that I won't pull on the England shirt again.
"This has been a very difficult decision, one of the toughest I've had to make in my career. I have agonized over this since coming back from Brazil and have spoken to family, friends and people close to me in the game before coming to this point.
"Most importantly, Brendan [Rodgers] has been fantastic and obviously I have to look after my body as much as possible to ensure I can give everything when I take to the field. To ensure I can keep playing to a high level and giving everything to Liverpool Football Club I believe this is the right decision, and having Champions League football back at Anfield is another big factor in my decision."
Gerrard made his debut for England in a 2-0 win over Ukraine at Wembley in 2000 and goes out as his country's third-most capped player behind only Peter Shilton and David Beckham.
He captained England on 38 occasions, with Gerrard paying tribute to current manager Roy Hodgson for handing him the armband.
"I'd especially like to thank Roy, firstly for giving me the captaincy permanently when he took the job, making me the proudest man in the country and allowing me to fulfill my childhood dream. He has been very understanding over the past few weeks and is a man I will always hold in the highest regard."
Hodgson acknowledged his disappointment in seeing Gerrard step down, but hailed his career, saying England had been "blessed" to have the midfielder.
He added: "While I'm disappointed in the decision, I can entirely understand Steven's situation and can have no complaints given the incredible service he has given to his country. I must respect his wishes due to the discussions we have had and the amount of thought and consideration he himself has given it.
"He is an incredible man and a fantastic footballer who we have all been blessed to see in an England shirt so often. It is never by coincidence that people reach such a staggering figure as 114 caps, it is a mark of his wonderful talent allied to a huge drive and determination to live up to the highest standard."