Fabio Capello resigned as England manager on Wednesday following the decision by the FA to strip John Terry of the captaincy because of his pending racism trial in July. Terry denies a charge of racially abusing QPR defender Anton Ferdinand in October.
Pearce, who served as Capello's assistant, is the England Under-21 boss and will take charge of the Great Britain men's Olympic team this summer, will look after senior national team affairs in the short term at least. He had been due to be in charge of the under-21s against Belgium in Middlesbrough on February 29.
Bernstein told a press conference at Wembley: "I can announce that Stuart Pearce will manage the England team against Holland.
"He has huge experience outside and inside the organisation. He has been working with the under-21 team and has been working with Fabio for some time. I have got great confidence in Stuart, we will be in good hands.
"Our priority then will be to appoint a new England manager."
Harry Redknapp has become the overwhelming favourite to succeed Capello in the long term.