Lighly spray a square casserole dish (9x9 inch or similar) with nonstick cooking spray.
In a medium saucepan, bring the water to a boil over high heat. Reduce the heat to medium and whisk in the polenta. Continue to whisk until the mixture starts to thicken, about 3 minutes. Add the bell pepper, olive oil, chives, salt and pepper to taste. Continue to cook, stirring, until the polenta is very thick, about 3 to 5 minutes more.
Pour the hot polenta into the prepared casserole dish and smooth over with a rubber spatula, about 3/4-inch thick. Allow the cake to rest for at least 30 minutes.
Cut the polenta cake into 3x3 inch squares and brush both sides lightly with extra-virgin olive oil.
Preheat a grill or grill pan until very hot.
Add the polenta squares to the pan and grill for about 3 minutes per side.
Carefully cut the squares corner to corner to form triangles, serve immediately.
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