The world's biggest online shopping event raked in more than $30.8bn (210bn yuan; £23bn) in sales in 16.5 hours of trading, surpassing last year's all-time-high.
A gala featuring pop star Taylor Swift launched the 24-hour shopping blitz.
It marked Alibaba's first Singles' Day since the exit of its colourful founder, Jack Ma.
He was replaced as executive chairman by Daniel Zhang earlier this year after stepping down to focus on philanthropy and education.
The firm said sales reached $1bn in a little over one minute of trading on Singles' Day.