Leaky plasmon modes (LPMs) in metal nanowires (NWs), which combine the physical characteristic of both “plasmonics” and “leaky radiation”, present distinguished performances in terms of guiding and radiating light. In contrast to traditional light‐guiding in metal NWs with one single LPM, multiple LPMs are crucial for advanced uses such as augmenting data transmission channels, enhancing sensing performance, manipulating polarization and converting mode. Here, we demonstrate experimentally the control over multiple LPMs in pentagonal silver NWs. By combining far‐field real‐space imaging and leakage radiation microscopy, the three typical LPMs with fields mainly concentrating in corners surrounded by air are specifically identified. By manipulating excitation wavelengths and NW diameters, the number of the excited LPMs can be controlled. These findings reveal the physics of LPMs in silver NWs, thereby paving the way towards applying the high‐order leaky modes in silver NWs for photonic integrated circuits, nanoscale confinement, plasmonic sensing, QD‐nanowire coupling, etc.