Having opened Group C with four wins from as many matches, it has long looked a case of when rather than if the Euro 2020 runners-up seal their place at next summer’s tournament in Germany.
England had won 21 of their previous 22 Euros qualifiers but had to make do with a point on Saturday evening having failed to build on Walker brilliantly cancelling out Oleksandr Zinchenko’s opener.
Ukraine were vastly improved from their meek March loss at Wembley and, despite being forced to play away from home due to the ongoing Russian invasion, received fantastic support in Wroclaw.
Skipper Zinchenko sparked ear-splitting celebrations when opening the scoring at the Tarczynski Arena, where world heavyweight champion Oleksandr Usyk beat Daniel Dubois a fortnight ago.
But this time there was no Ukrainian knockout blow against English opposition.
Harry Kane’s exceptional pass was met by a similarly impressive Walker touch, before the right-back coolly slotted home to open his international account on his 77th appearance.
The 33-year-old became the second-oldest player to score his maiden England goal after ending the longest wait for an outfield player to net their first for the country.
Bukayo Saka saw an effort tipped onto the bar as England pushed for a winner that evaded them.
As many as 300,000 Ukrainians are said to live in this region of Poland and there was a spine-tingling rendition of their national anthem by the wall of yellow and blue in the ground.
The atmosphere was wonderful but England looked unruffled by the partisan support, patiently probing as they sought to land an early blow.
But it soon became clear that their domination was passive and Ukraine appeared emboldened by their fans’ raucous backing whenever they got forward.
After a few moves broke down, their captain turned the volume up to the max in the 26th minute.
Georgiy Sudakov collected Walker’s looping header in his own half and drove inside and away from the attention of Saka, before playing wide to Viktor Tsygankov on the right.
The winger held up the ball under pressure before playing onto overlapping Yukhym Konoplya, whose cut back was driven home from eight yards by Arsenal midfielder Zinchenko.
It was a perfectly executed counter-attack and Ukraine’s celebrations were deafening.
England had been caught cold and Jordan Henderson – picked for the first time since his controversial move to Saudi Arabia – blazed over as they looked to hit back, with frustrated James Maddison booked for a poor challenge.
Lacking creativity and a cutting edge, Kane dropped deep and took it upon himself to spark England into life.
Ukraine stood off the striker and watched him fire an exceptional diagonal ball from just outside the centre circle over Everton left-back Vitaliy Mykolenko to Walker.
An expert first touch was followed by impressive composure and a smart finish from close range.
The England team charged towards Walker to celebrate – an effort cleared after a VAR review for offside.
Under-fire Harry Maguire, making his first competitive start of the season, headed over when play resumed and goalkeeper Georgiy Bushchan pushed away a threatening Henderson cross.
The Group C leaders were pushing to take the lead and Ukraine’s goalkeeper made a fantastic save in the 59th minute.
Kane played onto Saka and the Arsenal forward cut inside to unleash a left-footed strike from the edge of the box that Bushchan touched onto the bar.
Saka and team-mates soon saw appeals for handball in the box fall on deaf ears as Southgate’s men continued in the ascendancy.
Marcus Rashford and Phil Foden were soon introduced to add punch to their game, with Maguire having another headed attempt before being booked when attempting to prod in.
England looked most likely to score as the clock wound down but there was to be no winner.