A 50bn Zimbabwean dollar note was issued on Tuesday
Zimbabwe is introducing a Z$100 trillion note, currently worth about US$30 (£20), state media reports.
Other notes in trillion-dollar denominations of 10, 20 and 50 are also being released to help Zimbabweans cope with hyperinflation.
However, the dollarisation of the economy means that few products are available in the local currency.
On Thursday, the opposition leader said he was still committed to power-sharing intended to rescue the failing economy.
Since September, when the deal was signed, talks have stalled over who should control key ministries.
Movement for Democratic Change (MDC) leader Morgan Tsvangirai said he was due to hold talks with President Robert Mugabe "within this coming week" to try to resolve the political crisis.
He described Mr Mugabe as "part of the problem but also part of the solution".
The latest annual figure for inflation, estimated in July last year, was 231m% - the world's highest.
"In a move meant to ensure that the public has access to their money from banks, the Reserve Bank of Zimbabwe has introduced a new family of banknotes which will gradually come into circulation, starting with the Z$10 trillion," Zimbabwe's state-run Herald newspaper quotes a bank statement as saying.
But previous issues of new banknotes - and the dropping of several zeros from the currency - have done little to help Zimbabweans cope with inflation.
On Tuesday, a 50bn Zimbabwean dollar note was issued, less than a month after a Z$500m bill was released.
Correspondents say prices can double every day, and food and fuel - for those without US dollars - are in short supply.
Last month, the daily bank cash withdrawal limit - which at one stage was only enough for several loaves of bread - was abandoned.
However, most banks do not have enough cash to meet demand.
Some shops are licensed to sells goods in foreign currency but everyone from vegetable sellers to mobile phone service providers peg their prices to the US dollar.
Most groceries are brought in by Zimbabweans from neighbouring South Africa, Botswana or Zambia, further driving up prices.
There is more than 80% unemployment in the country and those with jobs find their salary is worthless unless they are paid in foreign currency.
Mr Tsvangirai is expected to return to Zimbabwe on Saturday after two months abroad.
At a press conference in Johannesburg, Mr Tsvangirai again appealed for prominent human rights activist Jestina Mukoko, who appeared in court on Thursday, and other such detainees, to be released.
Robert Mugabe has resisted growing calls for his resignation
"Those abducted and illegally detained must be released unconditionally if this agreement is to be consummated," Reuters news agency quotes Mr Tsvangirai as saying.
Ms Mukoko - director of the Zimbabwe Peace Project - denies charges of organising military training to topple President Mugabe.
She broke down in tears in court as she spoke about her ordeal when she was abducted from her home by armed security agents at the beginning of December.
She described how she was beaten on her feet during questioning.
"The experience was frightening. I would not wish it upon anyone," she said.
Under September's power-sharing agreement, Mr Tsvangirai is to become prime minister while Mr Mugabe remains as president.
But the deal faltered after the MDC accused Zanu-PF of keeping the most powerful ministries - including the one that controls the police - to itself.
As the political wrangling continued, Zimbabwe has been hit by a cholera epidemic that has claimed more than 2,000 lives, made worse by the collapse of the water, health and sanitation systems.
Mr Tsvangirai, and Western nations, accuse Mr Mugabe of not being sincere about power-sharing.
Mr Mugabe insists he welcomes the power-sharing deal, and has resisted growing international pressure to resign.