Shan Masood celebrates his century at Old Trafford, Manchester, on Thursday. Reuters
Left-handed opener Masood batted for nearly eight hours in largely bowler-friendly conditions for a Test-best 156, surpassing his 135 against Sri Lanka in Karachi in December.
He received excellent support from Shadab Khan (45) in a sixth-wicket stand of 105 that turned the tide after Pakistan had been struggling at 176-5.
The pair ran England ragged, with even defensive shots producing well-taken runs.
Pakistan had managed just 48 runs for the loss of three wickets in Thursday's first session to reach 187-5 at lunch.
But with five overs until the new ball, England captain Joe Root then bowled his own occasional off-breaks as well as frontline spinner Dom Bess immediately after the interval.
Shadab Khan sweeps as fielders take evasive action during play on the second day at Old Trafford. AFP
They bowled several loose deliveries to release the pressure on the batsmen, Masood and Shadab adding 27 runs in the first five overs after lunch.
Although Root took the new ball as soon as he could, with Pakistan 214-5 off 80 overs, the sixth-wicket pair were well set and the runs continued to flow.
There were no nervous 90s for Masood, who had been reprieved twice on 45 by Jos Buttler on Wednesday after the wicketkeeper dropped a catch and missed a stumping off the unfortunate Bess.
Two late-cut boundaries off Stuart Broad took him to 96 before twos off Broad and James Anderson saw Masood, who struggled during Pakistan's 2016 tour of England, to a 251-ball century, including 13 fours.
With the series being played behind closed doors because of the coronavirus, there was none of Pakistan's traditional enthusiastic crowd support to acclaim the landmark.
Instead, Masood's team-mates clapped and cheered the 30-year-old from the changing room balcony, with Pakistan great Younis Khan — now the batting coach — joining the applause.
Shadab Khan (R) looks on as Shan Masood reacts after reaching his century. AFP
As well as being his fourth hundred in 21 Tests, and a first against England, it was also Masood's third in a row, after his century against Sri Lanka was followed by 100 against Bangladesh in Rawalpindi in February.
Masood, educated in England, was the sixth Pakistan batsman to score a hundred in three consecutive Test innings after Zaheer Abbas, Mudassar Nazar, Mohammad Yousuf, Younis Khan and Misbah-ul-Haq.
All-rounder Shadab holed out off Bess with a mistimed slog to mid-on.
Fast bowler Jofra Archer then took two tail-end wickets with successive deliveries before Shaheen Afridi survived the hat-trick.
Masood, playing a textbook opener's innings, upped the tempo by hoisting and driving Bess for two sixes.
He eventually fell lbw after tea to Broad, having faced 319 balls, hitting 18 fours and two sixes.
Broad led England's attack with 3-54 from 22.3 overs while Archer also took three wickets.
Earlier Anderson, England's all-time leading Test wicket-taker, struck with just the sixth ball of the day when he had Babar Azam edging to Root at first slip on 69.
Pakistan and England cricket teams on Wednesday observed a one-minute silence before the start of the first Test at the Old Trafford as mark of respect for all those affected due to the COVID-19 pandemic.
"Fitness has been an important part of our strategy as a team since I took on the role of head coach last September and we have seen the benefits in the two Tests so far," Misbah wrote in a column for the Pakistan Cricket Board's website.
Pakistan Test captain Azhar Ali on Thursday lauded bowlers ahead of their series against England and stated he is lucky to have young pacers like Shaheen Afridi and Naseem Shah in the line-up.
Both Kings XI Punjab and Mumbai Indians (MI) will look to bounce back from their defeat and return to winning ways in the Indian Premier League (IPL) when the two giants face off in Abu Dhabi on Thursday.
Serena Williams suffered another blow in her bid for a 24th Grand Slam title as the American withdrew from the French Open on Wednesday with an Achilles injury, while 12-time champion Rafael Nadal and women’s top seed Simona Halep eased into the third round.
Manchester City announced the signing of Portuguese international centre-back Ruben Dias on a six-year deal from Benfica on Tuesday in the hope of solving the defensive problems that have dogged Pep Guardiola’s side over the past year.