As a schoolboy he displayed particular interest in geology and mineralogy. He left school in 1825 and in October, round about the time of his 15th birthday, he started attending classes at the local university, where he continued his studies till 1827. In September 1838 he relocated to Liverpool in England, there to establish, in the first instance at a rented refinery in Temple Street, a Liverpool branch of the family sugar business.
Macfie stood for election to the British parliament as the Liberal Party candidate in 1859, but failed to be elected.
He was more successful in 1868, and from November 1868 to February 1874 he served as a Liberal Party Member of the British Parliament, representing the constituency of Leith Burghs near to Edinburgh. As a Liberal Member of Parliament, Macfie took a particular interest in Postal Reform, but long before he entered parliament he held strong views on the subject.
As a young businessman based, by now, in Greenock, he responded with characteristic passion and at considerable length,in a letter dated 31 March 1838, to an invitation from a committee of London Merchants to provide information appropriately. His father returning from a business trip to London and finding that Macfie had been "meddling in public matters" in this way opined strongly that at the age of 26 the son was far too young for this level of involvement, and there is no record of Macfie having challenged his father"s judgement nor, in the immediate term, of his having again involved himself in public life.
On 17 May 1839 Macfie proposed marriage to Caroline Eliza Easton, daughter of Doctor John Easton of Edinburgh.
The marriage took place in Edinburgh in January 1840, following what was seen as an unusually long engagement. The couple produced 7 recorded children, born between 1840 and 1854 in Liverpool where Macfie was by now based.
20th United Kingdom Parliament.