Williams was handed an automatic place in the final after the world number one from Belarus reluctantly pulled out of their scheduled semi-final with a toe problem in order to regain fitness for the defence of her Australian Open title.
"Victoria has been nursing this injury for the past 10 days and it has continued to deteriorate to a point where she is unable to take to the court tonight [Friday]," tournament director Cameron Pearson told brisbaneinternational.com.au.
"We wish her all the best with her recovery and we hope to see her in Melbourne to defend her Australian Open title."
That meant the scheduled second semi between Pavlyuchenkova and Lesia Tsurenko was moved to the earlier time slot, and the former seemed to have more trouble adjusting before battling from a set down to win the match.
The match was an error-strewn affair and five of the first seven games went against serve before Tsurenko finally took a grip on the first set, winning it 6-4.
That was as good as it got for the world number 116, though, as Pavlyuchenkova dominated the remainder of the contest despite being unable to keep the mistakes out of her game.
The Russian broke to lead 3-1 in the second set, powered through the remainder of that set and then broke in the first game of the next.
The Ukrainian hit back straight away but Pavlyuchenkova reeled off four straight games to leave Tsurenko serving to stay in the match. She held to love and forced a break point in the next game, but Pavlyuchenkova produced a couple of big serves to drag herself over the line.
"I feel amazing," Pavlyuchenkova told Eurosport. "I didn't expect such a good start to my year and I'm pleased with what I've achieved in this tournament."
To test Williams, though, she will need to improve on a display which featured 37 unforced errors, five more than her tally of winners - although she acknowledged that her abbreviated preparations created difficulties.
"I like to have time before a match to relax," she said. "I had time do everything, but in a rush.
"I lost the first set and was missing some easy shots but I stayed calm for the whole match."