Charles Paine managed manufacturing and commercial enterprises before entering Vermont politics. His interests included a woolen mill, store and hotel at Northfield, where he also served as selectman and town meeting moderator. Elected to the Vermont House in the late 1820s, he brought the concerns of business, transport and public accounts into his political work.

As the Whig candidate for governor in 1841, Paine failed to obtain a popular majority, leaving the choice to the legislature, which elected him. Voters returned him for another term in 1842. His administration emphasized stricter accounting for public funds. He also proposed bringing colleges, academies and common schools within a more unified educational system, but did not secure the change. Declining another nomination in 1843, he concentrated on the development of railroads.

Paine founded the Vermont Central Railroad and became its first president. He placed the company's headquarters and repair facilities at Northfield, promising the town improved access to markets. Construction and expansion created large financial demands, and the company entered receivership after serious difficulties. His own fortunes were closely tied to the enterprise. Paine continued to seek opportunities in railway development, traveling to Texas in 1853 to investigate a possible southern route to the Pacific. He fell ill at Waco and died there in July. His career joined industry and state government to Vermont's early rail network.