Thaw the puff pastry according to the package directions.
Preheat the oven to 400°F (204°C) and line a large baking sheet with parchment paper.
Lightly flour a clean work surface and roll the puff pastry into a 10 x 12-inch rectangle.
Spread the pesto evenly over the pastry, leaving about a ½-inch border around the edges.
Sprinkle the grated Provolone cheese evenly over the pesto.
Add the freshly ground black pepper.
Scatter the chopped roasted red peppers evenly across the cheese.
Brush the top edge of the pastry with the egg wash.
Starting from the long side closest to you, tightly roll the pastry into a log.
Place the log seam-side down and refrigerate for about 1 hour until firm.
Trim the ends and slice the chilled log into ½-inch thick rounds.
Arrange the slices on the prepared baking sheet about 1 inch apart.
Brush the tops lightly with the remaining egg wash.
Bake the Cheesy Puff Pastry Bites with Pesto and Roasted Peppers for 16–18 minutes, or until puffed and beautifully golden brown.
Cool slightly, garnish with chopped fresh chives, and serve warm or at room temperature.