Following the completion of the 2001 Super 12 season, James was included in the Springboks squad and made his debut for South Africa at fly-half in a 32–23 loss to France at Ellis Park. In the following Test, also against France, he contributed five penalty goals in the 20–15 victory in Durban. After being omitted from the squad for the game against Ireland, James started in the first game against England. In the first half, he scored a try with the help of Jean de Villiers, and at the start of the second half he set up a try for Springbok wing Akona Ndungane, the first of his career
James was named in the Springboks squad for the 2007 Rugby World Cup. He played in three pool matches, including those against Samoa and England, and in all three games in the knock-out stages. In the final, against England, his composure and ability to nullify the impact of his opposite number, Jonny Wilkinson, helped South Africa to a 15–6 win
Following the 2007 World Cup tournament, James joined Bath Rugby. He made his debut in Bath's 28–6 victory over Auch in the European Challenge Cup on 10 November and was an immediate success, earning the man of the match award after scoring a superb individual try and setting up another with a deft cross-field chip-kick.
On 1 February 2011 it was announced that James would be joining the Lions back in South Africa at the end of May.
After his contract expired at the end of the 2012 season, he rejoined the Sharks.
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