She was first elected to the National Assembly of Quebec for the riding of Nelligan in a by-election held on September 20, 2004. She was re-elected in the 2007, 2008, and 2012 general elections. She was appointed Minister of Immigration and Cultural Communities in the minority government cabinet of Quebec PremierJean Charest in 2007 following the initiative of Jean Charest to represent Anglophones and Cultural Communities in his Cabinet. After Tony Tomassi's sudden resignation in 2010, she was given an additional role in cabinet as Family Minister. In August 2010, she retained the Family portfolio in a cabinet shuffle, but lost her culture and immigration duties to Kathleen Weil. When Parti Québécois leader Pauline Marois demanded that the province of Quebec have full control over its immigration, James replied that under a bilateral agreement with the national government, Quebec already has all the power it needs to select the economic immigrants it wants. James publicly entered the controversy over reasonable accommodation by stating that she stood by her decree to bar students from covering their faces with niqabs or burqas in French-language classes. She claimed that "There is no ambiguity about this question. If you want to assist in our classes, if you want to integrate into Quebec society, here are our values. We want to see your face." James' department decreed that Naema Ahmed leave CEGEP St. Laurent when Ahmed declined to remove her niqab during lessons. However, after James left provincial politics, she stated that her thinking on the niqab has evolved. The district of Saint Laurent, QC, where she sought a federal candidacy in a by-election, was 17-per-cent Muslim in the 2011 Census of Canada. On February 24, 2014, James announced she was leaving politics, and would not seek re-election in the 2014 election. On February 12, 2017, James confirmed on Twitter that would be seeking the Liberal Party of Canada's nomination for the Saint-Laurent federal electoral district. A 26-year-old high school teacher, however, defeated James for the Liberal nomination in that riding. Emmanuella Lambropoulos beat James and tax law professor Marwah Rizqy to secure the nomination.
Political commentator
James currently provides commentary to several CBC political programs, including as one of four former National Assembly ministers on the noonhour CBC Radio Canada program Le Club des Ex and as a member of the "Power Panel" on Power & Politics, an English-language political program on CBC News Network.