Volpi takes the senior role at Joost after 13 years at Cisco, where he was most recently senior vice-president and general manager for its routing and service provider technology group, and oversaw $11bn worth of business.
De Wahl, who remains with Joost as chief strategy officer, said: "Mike brings unparalleled leadership and technology expertise that will enable us to accelerate the growth of the company."
While at Cisco, Volpi was involved in around 70 acquisitions and was at one stage touted as a successor to Cisco CEO John Chambers, before quitting in February.
The move to appoint such a senior figure in the technology sector comes as Joost looks to court leading media firms to show their programming on its site. It is promoting itself as a safer alternative to YouTube, which has been dogged with controversy surrounding copyright issues.
Volpi said: "I am thrilled to have the opportunity to lead this team as the company embarks on its next critical stage of development."
Joost was founded last year and began broadcasting last month after securing around 30 advertisers, including Microsoft, Sony and Unilever.
Among media firms to sign up with Joost are Time Warner, Sony Corporation and MTV owner Viacom, which is currently involved in a legal battle with YouTube over alleged copyright infringement.
Joost was founded by Janus Friis and Niklas Zennstrom, who were also behind Kazaa as well as internet telephony service Skype, which Volpi was a board member of.
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