Born in London he was educated at Eton and Oxford, becoming a Fellow of All Souls College. He seems to have studied art while at Oxford under the tutelege of J B Malchair. He became the rector of St Erme, Cornwall but was often absent leaving the parish work to his curate. He embarked on numerous sketching tours around the British Isles and is one of many clergymen who were amateur artists. He remained as rector of St Erme for thirty two years before resigning in favour of his curate. By this time he had inherited the manor of Polsew in St Erme from his brother. Included in the estate was the library of his paternal grandmother's brother, Narcissus Luttrell. He sold some of the books, donated more to All Souls College, Oxford. The rest passed on his death in 1814 to E W Stackhouse of the Pendarves Estate, Camborne, a maternal cousin. E W Stackhouse's son changed his name from Stackhouse to Pendarves and added Wynne to his name in recognition of the important inheritance the family had received. The books inherited from Luttrell Wynne were sold as part of the Pendarves Library at Sotheby's in 1936. A group of Wynne's topographical drawings were sold privately when Pendarves House was demolished in 1958.

Luttrell Wynne was not a skilled draughtsman but was prolific and some of his sketches were used to make engravings where more proficient topographers' work was not available. On his death in 1814 he was buried in Westminster Abbey.