Playing for South Australia and Western Australia, he had a career spanning almost a decade. In that time, he was a consistent batsman, with a first-class batting average of 42.53. In the 1990s, James worked for the Seven Network in Adelaide. This included being a substitute sports anchor for the Seven Nightly News bulletin and working on local football discussion programs, such as Footy Plus.

In early 1998 James was teamed up with Amanda Blair and Paul Gale on Adelaide's SAFM, which eventually became that city's number one rating breakfast show. One memorable on-air incident at SAFM saw him covered in Adelaide Crow's bodypaint after the club he supports, North Melbourne, lost the 1998 AFL Grand Final to them.

In 2001 his big break came as the host of the Seven Network's Ashes (cricket) action with Jeff Thomson, but later moved to the Nine Network when the AFL was transferred. He became the nightly anchor for the National Nine News sports report, as well as contributing to other sports programs on the network, eventually becoming a regular commentator in both football and cricket coverage.

In 2005, James co-hosted Any Given Sunday with Garry Lyon and Sam Newman. In 2006, he (along with Garry Lyon) replaced Eddie McGuire as host of The AFL Footy Show, a position he currently holds. Additionally, he co-hosted the morning sessions of the 2006 Melbourne Commonwealth Games with Lyon, as well as the 2010 Winter Olympics and the 2012 London Olympics.

Apart from his television commitments, he works for radio station Triple M, as a host and commentator of their Australian rules football coverage. James was installed as Chairman of the North Melbourne Football Club on 6 December 2007 after the club rejected the AFL's deal to permanently relocate to the Gold Coast Brayshaw currently hosts the Sunday Footy Show, alongside panellists Brian Taylor, Nathan Thompson, Shane Crawford and Billy Brownless.

He has also hosted the Australian version of Wipeout with Josh Lawson. James is an accomplished and professional Master of Ceremonies and an engaging guest speaker, appearing regularly at corporate events as a keynote speaker or as the host at award nights, ceremonies and sports functions.