The blaze broke out at the Grand Diamond City hotel-casino in the border town of Poipet at about 23:30 (16:30 GMT) on Wednesday.
Around 400 people were in the building when it caught fire, police say.
Video circulating on social media shows what appeared to be people jumping or falling from upper floors.
Many Thai nationals were in the hotel, which backs onto the border, local media reports.
Authorities are still working to determine the cause of the fire.
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