In politics, he was both a Whig and a supporter of Catholic Emancipation and other Roman Catholic causes, which brought him into conflict with many members of his class in Ireland.
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In 1815 the parliamentary sketch-writer Thomas Barnes wrote of Mathew that he showed "...all the characteristic fervour of his countrymen in favour of the cause of the Catholics, but at the same time evinces a blindness of blundering greater than even foolish illiberality ever ascribed to his nation".
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During the present session of parliament, the speaker, having addressed the latter as the former, Montagu Mathew observed, it was strange he should make such a mistake, as there was as great a difference between them as between a horse chesnut and a chesnut horse.
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