Ali studied Medicine at University of New South Wales, graduating in 2002. He spent the majority of his training as a medical student and junior doctor locally at St. George and Sutherland Hospitals. He then undertook fellowships in Cardiac Electrophysiology and Pacing from January 2011 until August 2014 at Royal Prince Alfred Hospital, Sydney, and then The Heart Hospital, London, United Kingdom.

Ali was then appointed as Visiting Medical Officer at The Wollongong Hospital in January 2015 and commenced working at St. George Hospital in mid-2016. He has a special interest in diagnosis and management of heart rhythm disorders and performs electrophysiology studies, catheter ablations and device implantations.