He was a younger brother of Henry Pollexfen (1632-1691), of Nutwell in the parish of Woodbury, Devon, Lord Chief Justice of the Common Pleas.

He was active on various economic affairs committees, helping pass the Tobacco Act and renew the charter of the East India Company.

While there he participated in the recoinage debate, produced a report on the judicial system of Barbados and advocated a unified military command for the American colonies.

In 1677 he served on a special commission of the East India Company, accusing the directors of monopolising the trade through jobbery and refusing to issue new stock, and also condemned the export of gold bullion, which he saw as suppressing domestic production and employment.

After Charles Davenant published his An Essay on the East India Trade in 1697, Pollexfen responded with his essay England and East India Inconsistent in their Manufactures, and also published A Discourse of Trade and Coyn dated 15 July 1696,[7] an extended version of which was republished to counter William Lowndes proposal of recoinage.