James put down a solid first run to score 89.00 before turning it on in the second and final run of today's qualifiers.
The 23-year-old looked strong as he scored 96.75 to finish behind only one competitor - the USA's Shaun White who scored a near-perfect 98.50.
Callister was the final athlete through to the final having improved on his opener of 66.75 in his final run, scoring 77.00 to make it through to his second Olympic final.
Australia's other competitor in the event Nate Johnstone scored 62.25 and 10.25 to finish 22nd overall and not progress to the final.
Recent X-Games gold medallist Ayumu Hirano of Japan had the third highest score overall with a 95.25 on his second run.
James and Callister will be joined by all four USA representatives (White, Ben Ferguson, Jake Pates & Chase Josey), three Japanese athletes (Hirano, Raibu Katayama & Yuto Totsuka) as well as Jan Scherrer of Switzerland and Peetu Piiroinen of Finland.