"We are ready to start the games," Carlos Arthur Nuzman, president of the Rio 2016 Organizing Committee, said at a press conference in the city, adding that the event "could start today."
"They will be a maximum success in this beautiful city of ours," he said.
Speaking alongside him, Paes reiterated the announcement but cautioned that visitors should not expect to find a city that operates like Chicago, New York or London.
"Our development stage is different," he said.
The government later tweeted that every venue for the quadrennial event is ready, and the primary press center was open. It said there will be 85,000 security personnel at Olympic sites and important places like the city's airports.
Rio de Janeiro state, which controls the region's military police force, issued an executive order requesting emergency funds from the federal government to pay officers their bonuses and overtime.
The 2.9 billion-real bailout (roughly $850 million) was made available last week after acting Gov. Francisco Dornelles said the games could be a "big failure" without the funds.
It's believed that the back pay will be distributed this week.
"We are numbers, nothing more," one officer, who wished to remain anonymous, told CNN.
"You encounter a drug trafficker armed with lots of ammunition and you only have only 20 bullets. It is absurd."
Two officers, interviewed by CNN on condition of anonymity, said the city's scant resources are used to patrol tourist hotspots such as Copacabana instead of favelas where criminal gangs run the streets.
They have risked speaking out because they say they've watched fellow officers die to preserve Rio's image -- not to protect its people.
"We have a very common saying here in Brazil -- for the English to see," one of the officers said. "I believe that the politicians here are doing everything for the English to see."
Death rate rising
According to figures from Brazil's Public Security Institute published last week and distributed by Amnesty International,
on-duty officers killed 40 people in May alone -- police killed 17 people during the same period last year.
Last year, police killed at least 307 people in Rio -- a figure that accounts for one in every five homicides there, according to Amnesty.
According to the figures, police killed 645 people in the state in 2015, and many of the victims were young, black men from favelas and poor communities.
"Brazil has one of the highest levels of homicides in the world, with around 42,000 people killed with guns every year," Atila Roque, Amnesty International's Brazil executive director, said in a statement.
"Those living in the most marginalized areas of the city are disproportionally affected by this crisis."
When Brazil hosted the World Cup in 2014, police in Rio de Janeiro state killed 580 people, a 40% increase from the previous year, the rights group said.
Rousseff is accused of breaking budget laws, but she maintains she did the same things previous Brazilian leaders have done.
And on Tuesday, a group of Brazilian scientists announced it had detected a drug-resistant bacteria growing off the shores
of some of Rio's most iconic beaches.