Harry Kane scored either side of Harry Maguire's powerful header before Jordan Henderson's first England goal – in his 62nd appearance – sealed an emphatic quarter-final triumph in Rome.
England now heads back to Wembley for a semi-final clash with Denmark, which defeated the Czech Republic, on Thursday (AEST), with a first appearance in a final since the FIFA World Cup of 1966 in the offing.
While England's attack clicked, it is the Three Lions' defensive resilience which has seen them through, with Sunday's (AEST) win bringing up a seventh straight clean sheet.
It is the first time England has gone as many games without conceding a goal, with the run so far lasting 662 minutes.
Five of those clean sheets have come at this tournament, and no side has ever kept five successive shutouts to start a European championship campaign.
Pickford, who had a difficult 2020-2021 season with Everton – especially in the first half of the campaign – has played every minute.
Given his troubles for his club, doubts had been raised over Pickford's suitability for England's number one jersey, with Burnley's Nick Pope, who underwent surgery and missed out on Gareth Southgate's squad, and Manchester United's Dean Henderson raised as alternative options.
Yet Southgate kept faith with the former Sunderland goalkeeper, who has made nine saves from a total of 42 shots faced (including blocks) so far at UEFA Euro 2020.
Four of his saves have come from attempts inside the area, including a chance for Ukraine's Roman Yaremchuk early on in Sunday's (AEST) encounter, while the other five have come from long-range efforts.
As it was in the run to the 2018 FIFA World Cup semi-finals, Pickford's distribution has also been a key factor for England.
He has recorded 95 successful passes, with three of those ending in the final third, from 147 attempts, while he has found a team-mate with 32 long passes (as defined by Opta).
There was a nervy moment for Pickford in the second half at Stadio Olimpico, when he sliced an attempted clearance, but England's defence spared his blushes.
The 27-year-old may face an altogether tougher test against Denmark, however, with Kasper Hjulmand's team having scored 11 goals so far at UEFA Euro 2020. Only Spain, which plays Italy in the other semi-final, has managed more (12).