Kane was amongst the favourites to be handed the armband by manager Gareth Southgate, having carried out the role on numerous occasions under the current England boss.
"Harry has some outstanding personal qualities. He is a meticulous professional and one of the most important things for a captain is that they set the standard every day," Southgate said in a statement.
"He has belief and high standards and it is a great message for the team to have a captain who has shown that it is possible to be one of the best in the world over a consistent period of time and that has been his drive.
"Harry will need the support of the other good leaders we've got around him. You don't become a top team by just having a good captain with good values. That has to spread right throughout the group but I think he's the one ready to take that challenge on."
Kane, who will be appearing at his first World Cup, has scored 12 goals in 23 appearances for England.