He started mining copper at Coniston in the Lake District in 1756 and around the same time at Alderley Edge, Cheshire. In 1758 he built a copper smelter on Macclesfield Common using coal from a shallow outcrop outside the town. He entered into partnership with Brian Hodgson of Buxton, who had coal-mining interests at Disley. Roe then built brass-wire and rolling mills at Eaton near Congleton and at Bosley. Initially he bought copper ores from the Duke of Devonshire's mine at Ecton Hill, Staffordshire (see also Ecton Mines) but then extended his own mining interests to Penrhyn-Du in North Wales in 1763. In 1764 he obtained a 21-year mining lease from the Bayly family for Parys Mountain in Anglesey and for a lead mine in Caernarvonshire. In March 1768 a discovery was made of a very large deposit of copper ore, which was known as 'The Great Lode' and which turned the mine into the largest copper mine in Europe.