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1
Preheat oven to 325 degrees F. Lightly spray 4 heatproof 6.5-oz. ramekins with vegetable spray. Place ramekins in a casserole dish.
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2
Place 1/2 cup sugar in a small, heavy, dry skillet over medium heat. When sugar begins to melt around the edges, gently shake the pan continually, swirling sugar around, until all the sugar melts; don't use utensils to stir. When sugar is completely melted and dark brown, remove the pan from heat.
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3
Quickly pour equal amounts of caramel syrup into the 4 prepared ramekins.
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4
Place 1 egg and 3 egg yolks in a bowl with a pinch of salt and 1/4 cup sugar. Whisk until sugar is dissolved and mixture becomes frothy, about 1 minute.
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5
Spoon the creme fraiche into the egg mixture; add the milk, vanilla, and Grand Marnier. Whisk together until ingredients are completely mixed.
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6
Ladle mixture into the prepared ramekins, filling them about 2/3 to 3/4 full.
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7
Fill casserole with hot tap water to reach halfway up the sides of the ramekins. Place casserole on middle rack of preheated oven.
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8
Bake until just barely set, 45 to 50 minutes. You can start checking for doneness at about 40 minutes.
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9
Using tongs, remove the ramekins from the casserole to a cooling rack. When just slightly warm, run a sharp paring knife around the edge of each custard.
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10
To unmold, cover ramekin with a small plate, then invert. Chill before serving.
