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Place 240ml water, 200g caster sugar and 50g unsweetened cocoa powder in a medium saucepan over a medium heat.
Stir constantly until the sugar has dissolved and the cocoa powder is fully incorporated.
Bring to a gentle simmer, stirring occasionally, and let it bubble gently for about 2 minutes.
Remove the saucepan from the heat and leave the chocolate syrup to cool completely (about 30–45 minutes).
Once cool, stir in 5ml pure vanilla extract and 360ml vodka until well combined.
Using a funnel, pour the liqueur into a clean, airtight bottle or jar and seal it tightly.
Store in a cool, dark place. Use immediately, or leave for the flavours to develop for 1–2 days before serving.