"The basis for constructive dialogue has been undermined. It's impossible to have a constructive meeting tomorrow," Chief Secretary Carrie Lam told reporters.
Lam placed the blame for the collapse of the talks at the feet of student leaders who she accused of "undermining trust" in the proposed meeting with their comments over the last two days.
"The dialogue cannot be deployed as an excuse to incite more people to join the protest," she said.
Her comments came just hours after protest leaders vowed to ratchet up their occupation of key parts of the city if they failed to win concessions from the government.
Parts of the vital financial hub have been paralysed for more than a week by demonstrations calling for Beijing to grant the former British colony full democracy and for the city's Chief Executive Leung Chun-ying to resign.
Under plans unveiled by China in August, Hong Kongers will be able to vote for Leung's successor in 2017, but only two to three vetted candidates will be allowed to stand.