The objective of this work was to gain insight into the operating conditions that affect the efficiency of ultrasound-assisted extraction (UAE) parameters to achieve the best recovery of bioactive compounds from broccoli leaf and floret byproducts. Therefore, total phenolic content (TPC) and the main sulfur bioactive compounds (sulforaphane (SFN) and glucosinolates (GLSs)) were assayed. Distilled water was used as solvent. For each byproduct type, solid/liquid ratio (1:25 and 2:25 g/mL), temperature (25, 40, and 55 °C), and extraction time (2.5, 5, 7.5, 10, 15, and 20 min) were the studied variables to optimize the UAE process by using a kinetic and a cubic regression model. TPC was 12.5-fold higher in broccoli leaves than in florets, while SFN was from 2.5- to 4.5-fold higher in florets regarding the leaf’s extracts obtained from the same plants, their precursors (GLS) being in similar amounts for both plant tissues. The most efficient extraction conditions were at 25 °C, ratio 2:25, and during 15 or 20 min according to the target phytochemical to extract. In conclusion, the type of plant tissue and used ratio significantly influenced the extraction of bioactive compounds, the most efficient UAE parameters being those with lower energy consumption.