Last year's champion Shahjalal and runner-up Jibon Boli did not participate in this year's competition
The match with be the 36-year-old Williams' first in almost a year as she prepares to try to defend her Australian Open crown in January, a title she captured earlier this year while pregnant.
"I am delighted to be returning to the court in Abu Dhabi for the first time since the birth of my daughter in September," Williams said in a statement on the championship's website.
Williams and Ostapenko will be the first women to participate in the 10th edition of the Mubadala World Tennis Championship, which has long marked the beginning of the men's global tennis season.
"I am excited and honoured to be making my comeback as part of the first women to participate in the event," Williams added.
The championship runs from Dec 31 to Jan 2