In a small pot combine 1/3 cup sugar, orange zest, 1/2 the habanero and 1/3 cup water. Bring to a simmer over medium heat and continue to cook, stirring occasionally, until the sugar is dissolved and the pepper is softened, 3 to 5 minutes. Set aside to cool completely; strain.
Mix the remaining 1 tablespoon sugar and salt together in a shallow dish. Run a lime wedge around the rim of two lowball or margarita glasses and then run the cut side of the remaining 1/2 habanero around the rim. Roll the moistened rims in the sugar and salt mixture until well coated. Add ice to the glasses.
In a cocktail shaker filled with ice combine the tequila, lime juice, triple sec and 1/4 cup of the orange habanero syrup. Shake until well combined and strain into the prepared glasses. Garnish with a lime wedge and a thin slice of habanero.