Drain the tofu and place the slices on a tea towel or paper towels; cover with another towel and press gently to remove excess water. Transfer the pressed tofu to a shallow dish in a single layer.
In a small bowl, whisk together the soy sauce, rice vinegar, and sesame oil. Pour the marinade over the tofu, flip gently to coat both sides, and marinate at least 10 minutes or up to overnight. Reserve the marinade.
Heat a large skillet over medium-high heat and spray with avocado oil. When hot, add the tofu and brown about 2 minutes per side until golden.
Meanwhile, warm the cooked brown rice (or microwave frozen rice) and toss the broccoli with any remaining marinade. Microwave the broccoli 1 minute or steam until tender-crisp.
Assemble bowls: divide 1/2 cup rice between two bowls, add the edamame and steamed broccoli, and place 2 tofu slices on each bowl. Drizzle 1 teaspoon chili oil over each bowl (or to taste) and garnish with chopped scallion.