[3] His first marriage enabled Buckley-Mathew to enter politics, becoming a Conservative Member of Parliament for the Irish constituency of Athlone at the 1835 general election.
[4] At the following election, he instead stood for Shaftesbury but, on the initial count, was unsuccessful, losing to the Whig John Sayer Poulter.
His career in the Americas lasted some length; he was consul at Charleston, South Carolina, between 1850 and 1853, and then at Philadelphia, Pennsylvania in 1853, only ending in 1856 when his exequatur was removed by then-President of the United States Franklin Pierce.
He then served in the Black Sea between 1856 and 1858, and became secretary and chargé d'affaires of the legation in Mexico and then for other Central American republics, the latter where he was minister from 1861 to 1863.
The estates, from Abednego Mathew (died 1837), cousin to his father, were on St Kitts, and at Lyth near Ellesmere, Shropshire.