Heat 2 tablespoons (30 ml / 1 fl oz) of the olive oil in a large skillet over medium-high heat.
Add the mushroom slices in a single layer (work in batches if needed) and sear until golden brown on both sides.
Season the mushrooms with salt and pepper, then drizzle with the balsamic vinegar.
Cook for another minute until the vinegar has reduced and the mushrooms are tender, about 5 minutes total.
Transfer to a plate to cool.
While the mushrooms cool, prepare the olive salad.
In a medium bowl, combine the chopped olives, roasted red peppers, peperoncini, tapenade, sun-dried tomatoes, and the remaining 2 tablespoons (30 ml / 1 fl oz) of olive oil.
Season with salt and pepper and stir to combine.
Prepare the bread by carefully slicing the loaf in half horizontally with a serrated knife. To make room for the generous filling, gently scoop out some of the soft interior from both the top and bottom halves.
Assemble the sandwich. Lightly drizzle the cut sides of the bread with olive oil.
Spread half of the olive salad mixture over the bottom loaf.
Arrange the cooled portobello mushroom slices in an even layer on top.
Spread the remaining olive salad over the mushrooms.
Place the top half of the bread on top and press down gently. For the best flavor, wrap the entire loaf tightly in plastic wrap and let it sit for at least 30 minutes before serving. To serve, unwrap and cut the loaf into 4 equal wedges.
Don't be afraid to customize the olive salad.
Add a tablespoon of capers, a pinch of red pepper flakes for heat, or some chopped fresh parsley for brightness.