Steps:
- Preheat oven to 450°. Remove tender leaves from broccoli stems; wash leaves and set aside. Separate florets from large stems. Leaving some stem attached, cut enough florets into 1" pieces to measure 4 cups (set aside remaining florets for another use). Cut bottom 1" from stems and discard. Using a vegetable peeler, remove woody outer layer to expose the pale-green center (you'll need to remove 2-3 layers). Quarter stems lengthwise. With the tip of a paring knife, make shallow crosshatches into flat sides, if desired (this increases surface area, allowing broccoli to absorb more flavor). Place florets on a rimmed baking sheet; drizzle with 2 Tbsp. grapeseed oil and toss to coat. Season with salt and pepper. Roast florets, turning once, until charred, 15-20 minutes. Let cool; mince florets. Whisk shallot, vinegar, and lemon zest in a medium bowl. Gradually whisk in olive oil, then minced florets. Season vinaigrette to taste with salt and pepper. Toss broccoli stems and remaining 1 Tbsp. grapeseed oil in a large bowl. Heat a large skillet over medium-high heat. Working in batches, sear stems on all sides until browned in spots and crisp-tender, 3-4 minutes per batch. Divide among plates. Drizzle with vinaigrette and garnish with reserved broccoli leaves.
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