On Friday, Mathieu Vandal decided to resign because he could no longer ensure the integrity of the review process, he told Radio-Canada.
Vandal said he is also suspicious of the voters list in other Montreal ridings.
Parti Québécois leader Pauline Marois said she is concerned about the possibility of voter fraud.
"It raises very serious questions. I am asking the Chief Electoral Officer to address it ... but this is a situation that worries me," she said at a news conference in Rivière-du-Loup.
How to register for the electoral roll?
To vote, you must be registered on the electoral roll and fulfill the following conditions for the vote on 7 April 2014:
-Be aged 18 or over;
-Be a Canadian citizen;
-Be domiciled in Quebec for six months.
Source: Chief Electoral Officer of Quebec
The returning officer for the Sainte-Marie-Saint-Jacques riding, Ian Parenteau, confirms that there has been an influx of anglophone and allophone students who wish to register on the electoral roll, but sees no evidence of fraud.
"There is no fraud, but there is a potential," said Parenteau.
Some 75 per cent of voters in the riding of Sainte-Marie-Saint-Jacques consider French to be their "first official language spoken," according to the latest Statistics Canada census.
Parenteau said the situation highlights the difficulty for reviewers to judge what qualifies as valid documentation and proves that a person's "domicile" has been in Quebec for six months.
There have been reports of Montreal university students from out-of-province saying they feel they are being prevented from voting in the upcoming Quebec election.
The deadline to register to vote is April 3 at 2 p.m. ET.