Volpi cited "personal reasons" for his resignation. He will be replaced by Charlie Giancarlo, who also heads up Cisco's Scientific Atlanta and Linksys divisions, and acts as the company's chief development officer.
Both Volpi and Giancarlo have been suggested as potential replacements as Cisco's chief executive. Volpi will stay on in a consulting role pending the transition of his tasks to Giancarlo.
The resignation comes days after Cisco reported record revenues, which in part were fuelled by a high demand for routers from online video services.
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