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In a medium saucepan, combine 1 cup water, 1 cup granulated sugar, and 0.5 cup unsweetened cocoa powder over medium heat.
Stir constantly until the sugar dissolves and cocoa powder is fully incorporated.
Bring the mixture to a gentle simmer, stirring, and let it bubble lightly for 2 minutes.
Remove the saucepan from heat and let the chocolate syrup cool completely (about 30–45 minutes).
Once cool, stir in 1 teaspoon pure vanilla extract and 1.5 cups vodka until fully combined.
Using a funnel, pour the liqueur into a clean airtight bottle or jar and seal tightly.
Store in a cool, dark place. Use immediately or let flavors meld for 1–2 days before serving.