Chief Executive Leung Chun-ying told reporters that he has asked the territory's top civil servant to arrange talks with the protesters, who have been demanding electoral reforms. The massive street demonstrations are the biggest challenge to Beijing's authority in Hong Kong since China took control of the former British colony in 1997.
Leung made the comments in a news conference just minutes before a deadline that had been set by the protesters for him to step down.
During the day, the protesters prepared face masks and goggles while police brought in supplies of tear gas and other riot gear as tensions grew in an increasingly tense standoff outside the imposing government compound near the waterfront.
Police warned of serious consequences if the protesters tried to surround or occupy government buildings. The protesters threatened to do so if Leung didn't resign by the end of Thursday.