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James was approached by a talent agency for her first experience with the adult industry. Her job was as a model passing out fliers at the Erotica LA convention in 2006. Later, she was approached by a friend to appear in an adult movie and her adult film career began. She was in the adult industry for a year before she signed an exclusive three-year performing and directing contract with SexZ Pictures. Paulina's first anal scene was in The Perils of Paulina with Evan Stone.
In March 2008, James announced she was taking a one-year hiatus "due to my pregnancy with my wonderful fiancÃ©".
"I planned to do big things with SexZ Pictures this year and in the years to come, but as we speak I will be taking time off due to my pregnancy," James said in a statement.