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Combine powdered sugar, cocoa powder, chocolate, cornstarch, and sea salt in a food processor. Scrape in vanilla seeds; discard pod. Blend until mixture is smooth and powdery, about 1 minute.
Bring milk to a simmer in a small saucepan over medium heat. Whisk in 3 Tbsp. hot chocolate mix and cook, whisking occasionally, until mixture returns to a simmer and hot chocolate mix is dissolved and thickens slightly, 1-2 minutes.
Transfer hot chocolate to a mug. Top with whipped cream and marshmallows and dust with cocoa powder.
Hot chocolate mix can be made 2 months ahead. Store in an airtight container at room temperature, or freeze up to 3 months.