Shahzad, 33, replaces another former Yorkshire player, Steve Kirby, who left in October to join Derbyshire’s coaching staff.
Born in Huddersfield, Shahzad turned to coaching when he ended his professional career in 2017.
The former fast bowler, who played for Yorkshire until 2012 and then for Lancashire, Notts, Sussex and Leicestershire, was head coach of senior cricket at Ampleforth College in York.
Shahzad had been working alongside Kirby at MCC as a one-day specialist bowling coach, a role that developed into assistant coach of MCC Young Cricketers.
Now he will lead that young cricketers’ programme, which has been running since 1972 and provided a platform for players such as Ian Botham, Phil Tufnell and Mark Waugh, and will also provide elite coaching in the MCC Cricket Academy.
“It is a huge honour to be appointed to the role,” said Shahzad, who played one Test, 11 one-day internationals and three T20 internationals for England.
“There has been a lot of hard work behind the scenes but it’s all been worth it, and now I’m looking forward to the years ahead.
“I believe that the 16 years of experience in international and county cricket I have is invaluable, and I am sure that this will be of benefit to the MCC Young Cricketers.
“Our job as coaches and mentors is to help these young players both on and off the field.
“We know enough as a coaching group to help them on the cricketing side, but it is that personal touch that counts.”
Shahzad went on: “2019 is a massive year at Lord’s, and with so much international cricket taking place, it’s an opportunity for the Young Cricketers to eat, live and breathe what they want to become.
“The YC’s programme is looking to help players who have missed the opportunity through their county age groups, or been involved with counties and not really progressed. We can potentially give them a second chance.”
John Stephenson, MCC assistant secretary (cricket), said: “After a rigorous recruitment process, we are thrilled to be able to announce Ajmal as our new head coach.
“His energy, passion and enthusiasm is evident and with him being fresh from the professional game, I am sure that he will be successful in driving forward the club’s coaching structure.”
Shahzad played 45 first-class games for Yorkshire, taking 125 wickets at 33.56 and scoring 1,145 runs at 26.02.
In 30 List A games he claimed 34 wickets at 34.76, and in 22 T20 contests he captured 17 wickets at 33.88.