Goals from Harry Kane and Bukayo Saka mean Gareth Southgate’s side have two wins from two at the start of qualifying for Euro 2024 following the 2-1 defeat of Italy on Thursday.
Jack Grealish was a late substitute at Wembley while Kalvin Phillips stayed on the bench after playing an integral role in Naples.
Phil Foden was unavailable after having surgery for acute appendicitis.
Ukraine gave as good as they got in the opening half hour with Stones and Walker part of the defence on hand to deny Chelsea winger Mykhaylo Mudryk, Marseille man Ruslan Malinovsky and Club Brugge forward Roman Yaremchuk.
However, England were in control from the moment Kane tapped home a whipped cross in the 37th minute.
It was two before half-time with in-form Arsenal man Saka turning and shooting from the edge of the box.
England dominated possession for much of the second period, with Stones and Walker tasked with bringing the ball forward from the back.
Grealish replaced Leicester’s James Maddison in the 85th minute and forced Ukraine goalkeeper Anatolii Trubin into a strong save in added time.
Luxembourg 0-6 Portugal
Bernardo Silva scored one and assisted another as Portugal were convincing winners at Luxembourg.
Ruben Dias also played the full 90 minutes.
Four goals came in the first half with Bernardo having a hand in the two that came between both Cristiano Ronaldo efforts.
It was his cross headed home by Joao Felix in the 15th minute and then creator turned provider a few minutes later when our No.20 turned a Joao Palhinha ball in.
Porto midfielder Otavio and AC Milan forward Rafael Leao added two more to complete the scoring deep into the second half.
That leaves Portugal with six points from their first two matches.
Northern Ireland 0-1 Finland
EDS captain Shea Charles played the first 70 minutes at the base of Northern Ireland’s midfield as they fell to a 1-0 defeat against Finland in Belfast.
It follows Thursday’s 2-0 victory over San Marino.
19-year-old Charles made his senior debut for Northern Ireland last May and has now represented the nation five times.
England, Portugal and Northern Ireland are not in action again until after the end of the 2022/23 club season.