"We want to work much more closely with Israel on innovation and technology," said Mr Cameron, praising the "countless talented young people in both our countries".
Mr Cameron, who made the announcement at the Conservative Friends of Israel lunch, spoke of Mr Klein's "huge experience in early-stage investment".
"I have worked in tech in both the UK and Israel, and I know that there is a huge potential synergy between our two tech economies," said Mr Klein. "Britain could get a huge economic boost by partnering up with Israeli tech. Israeli innovation could benefit from using Britain's global reach, world-class companies, our scientific base, our capital markets and our business development expertise.
He added that it was appropriate that the UK's first ever Tech envoy should be to "the Start-Up nation," as Israel has been dubbed.