Kane had a 104th-minute penalty saved by Kasper Schmeichel before converting the rebound to send England into their first major tournament final since the 1966 World Cup.
Italy lie in wait after a tense, pulsating semi-final under the arch on Wednesday night, when Simon Kjaer’s own goal cancelled out a superb Mikkel Damsgaard free-kick before Kane sealed a 2-1 extra-time win after his penalty was saved.
The final whistle sparked pandemonium in the ground and across the nation as dreams of football coming home edged closer to reality, 25 years on from Southgate’s penalty miss at this stage of the competition against Germany.
England made a start as electric as the atmosphere at Wembley, but Damsgaard’s stunning 25-yard free-kick silenced the home support as the 21-year-old continued to shine in place of the sadly absent Christian Eriksen.
It was the first goal England had conceded during an unusually straightforward summer, but they responded well to the setback and Kjaer turned teenager Bukayo Saka’s cross into his own goal under pressure from Raheem Sterling.
Schmeichel had superbly denied the latter moments earlier and the goalkeeper shone throughout a second half in which the video assistant referee cleared a Christian Norgaard challenge on Kane in the box.
The Denmark goalkeeper continued to impress in extra-time but could not stop England progressing to the final, with Kane slotting home after the Leicester man saved his initial spot-kick after Sterling was fouled.
Additional reporting by PA.