This marks the third time the government has extended use of the bill, owing to Venezuela's inability to distribute larger denominations of its embattled currency.
New denominations will enter circulation Monday, Maduro said. The 100-bolivar bills will remain in use until February 20, he said.
At the highest government exchange rate -- of about 675 bolivars per US dollar -- 100 bolivars are worth less than 15 cents.
A piece of bread in Venezuela costs about 500 bolivars.
The move comes a week after Maduro announced he was hiking the minimum wage for the fifth time in a year, this time by 50%.
Venezuela's minimum wage, including food subsidies, is rising to 104,358 bolivars a month, or $31 a month, according to the unofficial exchange rate on DolarToday.com.
The minimum wage was previously increased in October, when the government raised it 40%.
Exorbitant food prices and massive shortages of food and medicine have plagued Venezuelans for years, and the situation worsened in 2016. Inflation in Venezuela is expected to be 1,660% in 2017, according to the International Monetary Fund.
The country has been in recession for three years.
Opposition lawmakers have announced they plan to push for impeachment proceedings against Maduro at the National Assembly level after Venezuela's National Electoral Council halted a drive to hold a recall referendum on Maduro.
Maduro has called such attempts a "coup d'etat."
The President last week announced the creation of a "Special Anti-Coup Commission," which will be led by newly appointed Vice President Tarek El Aissami.
"This group will be dedicated 24 hours a day to take preventive, legal and corrective measures against all sectors wanting a coup and internal, political and economic terrorists," he said.
Maduro added the commission would "give peace and stability to the country."
Opposition Parliament members seeking to oust Maduro said, however, "There has been a breakdown of constitutional order and a continued state of coup led from the highest level of government by President Nicolas Maduro."
The commission will have members of the Venezuelan armed forces and police forces throughout the country.