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Combine cocoa powder, sugar, and milk in a medium heavy saucepan. Bring to a boil over medium heat, stirring from time to time.
Rinse and drain rice in a fine strainer. Add water, salt, and rice to a medium heavy saucepan.
Bring to a boil over high heat, then add milk mixture to rice. Reduce heat and cook uncovered at a gentle simmer, stirring frequently to keep rice from sticking to bottom of pan, until rice is tender and the consistency of a thick porridge (~25 mins).
Remove pan from heat. Add bittersweet and unsweetened chocolates and stir until completely dissolved. Let cool for 10 mins, then stir in vanilla. Taste and add more sugar and/or salt if needed.
Transfer to a serving dish or divide among individual dishes. Serve warm, at room temperature, or lightly chilled. Top with cream/crème fraiche and sprinkle with chocolate, as preferred.
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