The Leeds Rhinos skipper made his debut for England in 2000 and was capped 26 times, as well as a further 14 appearances for Great Britain.
A veteran of three World Cup campaigns, Sinfield scored 176 points for England and the 33-year-old underlined the difficulty he had experienced in coming to the decision.
"This is a decision I have taken a great deal of time over and it has been the toughest of my professional career," he said.
"I have always loved playing for my country, whether for England or Great Britain, and it has been a privilege and honour to lead my country for the last two seasons.
"I would like to thank Steve [McNamara, England coach], not only for choosing me to captain England, but also for the support and guidance he has given me over the last few years.
"I would like to thank my family who have always supported me throughout my international career and all the England and Great Britain coaches I have worked under and of course my England and Great Britain team-mates.
"The World Cup last year was a major step forward for the England team and the support we received reached a new level. I would like to thank the England and Great Britain fans who have always given me their support and I am sure more successful times are not far away."
McNamara, meanwhile, paid tribute to Sinfield and the example he set throughout his international career.
"Kevin is the ultimate rugby league professional and it has been a privilege to work with him in the last few years, when his attitude, application and enthusiasm have rubbed off on everybody," he said.
"His contribution and commitment to the England programme has been exemplary. I know that he has not taken this decision lightly and having spoken to him at length in the last few days I fully understand his reasons for calling time on his international career.
"Kevin's achievements with Leeds Rhinos are well documented and this decision will allow him to focus fully on extending his record as the club's most successful captain."