 James was educated at the Edinburgh Institution and King's College London before returning to Edinburgh in 1857.After several years in Scotland working first for the paper manufacturers Cowan & Sons, and then for stockbroker Robert Allan, he joined the Bank of New South Wales' London branch in March 1860; his cousin, Thomas Walker, was one of the bank's directors.In January 1862 he departed for Melbourne on "Swiftsure" and was posted to the bank's Sydney office.