Fire up a grill or grill-pan to medium-high heat. Grill the pineapple, turning once, until marked on both sides, about 1-2 minutes. Cut the pineapple into 4 pieces and set aside.
On a small plate add Limón-Chile seasoning and evenly spread it around.
Run an orange wedge along the rim of the cocktail glass until wet. Turn the glass and dip it into the the small plate with the Limón-Chile seasoning. Tap the glass into the seasoning until the rim in fully covered. Set the glass aside.
In a cocktail shaker, muddle together lime juice, orange juice, pineapple juice, agave, and 3 chunks grilled pineapple.Add mezcal, tequila, and ice; shake well. Strain into seasoned glass over ice. Garnish with grilled pineapple and orange wheel.