Huge throngs who have shut down central areas of the city with mass sit-ins all week had set a midnight deadline for Chief Executive Leung Chun-ying to step down and for Beijing guarantee the former British colony full democracy.
But moments before the deadline was set to expire, Leung appeared before reporters and flatly rejected those demands.
"I will not resign because I have to continue with the work for elections," he said, referring to upcoming polls in 2017 which are at the centre of the ongoing confrontation between demonstrators and the Beijing-backed city authorities.
In August, China said Hong Kongers would be able to vote for their next leader but only two or three candidates vetted by a loyalist committee would be allowed to stand.
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Demonstrators have dismissed the decision as "fake democracy" and have vowed to keep people on the streets for as long as it takes.
Loud boos and jeers echoed across the main protest site as Leung's words were relayed through a series of loudspeakers, AFP reporters said.
Protesters had vowed to escalate their occupation of major sites if their demands were not met but some said they would wait for more details before acting.
"We'll hear what the government has to say first and then plan our next steps," protester Stephen Chan told AFP shortly after Leung spoke. "People won't attack the police without provocation. I believe in the Hong Kong people's spirit."
Pictures shared widely on social media and television showed one barrel carried by police with the words "Round, 38mm rubber baton multi" written on it. Another had "1.5 in, CS" emblazoned on it, a possible reference to tear gas.