Republican Piyush 'Bobby' Jindal (32), if he wins, will make history as the first Indian American governor of a US state while a victory fir Democrat Kathleen Blanco (60) will make her the first female governor of a state in America's deep south that has seen only white men fill the post since the 19th century.
The polls, which will also elect a new state legislature, prosecutors and a lieutenant governor, started at 6 am (1730 IST) and is scheduled to close at 8 pm (0700 IST Sunday).
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Jindal's support stems from a combination of educated white conservatives drawn by his skills as a technocrat, working class whites and a section of blacks.
Black voters, who constitute 30 per cent of the electorate and traditionally voted for Democrats, hold the key, experts opined.
Unlike past Republican candidates, Jindal has made inroads among black voters with the state's leading black politician, New Orleans Mayor Ray Nagin, extending support to him.
Jindal worked in the Bush administration and was Louisiana's secretary of health and hospitals under outgoing governor Mike Foster.
Blanco is from Louisiana's French-influenced Cajun community. She has been in public life for 20 years and, at present, is the Lt Governor of Louisiana.