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.
Harry Redknapp has become the overwhelming favourite to succeed Capello in the long term.
But 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."
Bernstein revealed that the decision to strip Terry of the captaincy had been a unanimous one.
"We all believed that the John Terry case would be dealt with in March or April," Bernstein said.
"When it was postponed we were taken by surprise like everybody else was taken by surprise.
"The board made a very quick and unanimous decision regarding the captaincy. I informed Fabio on Thursday evening as soon as the decision had been made. Fabio wasn't happy but he accepted the board's authority in the matter.
"On Sunday Fabio conducted an interview with an Italian broadcaster. That caused conjecture and huge public debate and frankly it was an unsatisfactory situation."
Bernstein insisted Capello had "behaved with dignity and honour" during the meetings with the FA yesterday.
"Yesterday was not an easy day but we concluded matters with a handshake. Any reports of storming out and are a complete misrepresentation of the facts," he added.
"(FA general secretary) Alex Horne and I met with Fabio yesterday and had a meeting lasting just over an hour. It was a very detailed meeting with a lot of detailed questions asked by us. We then adjourned the meeting and I then engaged myself with Fabio in his office, and it was at that time that he offered his resignation and I, on behalf of the board, agreed that this was the right decision by the FA.
"I will emphasise that the meetings were professional and amicable."
He continued at the Wembley press conference: "Of course it's regrettable when a manager leaves like this. Fabio has had a great record, but it's happened now.
"Could it have been avoided? We had a very frank meeting with Fabio. It was very civilised and at the end of it he decided he felt he had to go. I can't really add to that."
Pushed as to why he accepted Capello's resignation, he replied: "I accepted it really for the reasons that were covered in the statement we put out yesterday.
"The matter arising from the English team captaincy issue and from Fabio's statement on Sunday and the consequential issues meant that I felt when Fabio offered the resignation it was in the interests of the FA and English football the right thing to do."
On the prospect of sacking the Italian, he said: "That just didn't arise. We had a full and frank discussion with him and he came to that conclusion himself."