The new 100g bar will be a mix of creamy milk chocolate with a hint of Marmite's famous yeasty spread.
Like Marmite's advertising slogan, the brand extension is likely to prompt a mixture of "love it" or "hate it" reviews.
Unilever, owner of Marmite, is marketing the Very Peculiar chocolate bar as a "devious treat for the in-laws" at Christmas or for those struggling to find a present for a loved one.
Initially available just for Christmas, Unilever said its potential success could mean it is a permanent addition to the line.
The Very Peculiar chocolate bar will hit stores, including BHS and Debenhams, on 4 October, supported by in-store activity and a PR campaign.
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