As a highly efficient and energy-saving cavitation method, Venturi cavitation is widely used in many industrial fields. This study synchronously investigated the cavity behavior and its corresponding wall static pressure characteristics in Venturi channels with various divergence angles to research the role of the divergence angle in cavity shape and the wall static pressure oscillation. Five rectangular Venturi channels with different divergence angles (4°, 6°, 8°, 10°, and 12°) were tested at the cavitation number (0.3–1.0). Based on the dynamic behaviour of gas–liquid interface, three cavity shedding types were identified: front shedding (I), central shedding (II) and tail shedding (III). A modified correlation for predicting average cavity length was proposed with the consideration of the effect of the divergence angle. Combined with the wall static pressure characteristics, as the divergence angle increased, the wall static pressure fluctuation in the Venturi became more intense. According to the wall static pressure oscillation characteristics, for the larger divergence angles (θ = 6°, 8°, 10° and 12°), the wall static pressure oscillation frequency was the same as the cavity shedding frequency and increased with the increase of the divergence angle. For smaller divergence angle (θ = 4°), no definite periodicity in pressure oscillation frequency could be observed.