Remove the peels from the citrus carefully, making sure not to include any of the pith. Place the peels in a large container and add the vodka (reserve the vodka bottle for later). Infuse until the alcohol strips the oils and color out of the peels, 12 to 24 hours.
Meanwhile, make the simple syrup. Combine the sugar and 1 cup water in a small saucepan and bring to a boil. Cook, stirring, until the sugar dissolves. Remove from the heat and let cool completely.
Fill the vodka bottle with about 27 ounces of the infused vodka and 7 ounces of the simple syrup and place in the freezer. Serve ice cold in chilled small copita or shot glasses.
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