Smith fronted Google's acquisition of major platforms including Google Earth, Google Maps and Picasa, and has been active in gay, lesbian and trans-sexual rights, a key social policy goal for many members of the Obama administration.
(Also see: Obama Tech Policy Maven Moves to Silicon Valley Role)
"Megan has spent her career leading talented teams and taking cutting-edge technology and innovation initiatives from concept to design to deployment," Obama said in a blog post on the White House web site.
"I am confident that in her new role as America's Chief Technology Officer, she will put her long record of leadership and exceptional skills to work on behalf of the American people."
In his two successful presidential campaigns, Obama was known for the pioneering use of computer and software technology but revolutionizing the government's use of such tools has proven a harder task.
The botched rollout of his signature health insurance law was largely owing to a malfunctioning website which caused a prolonged political headache for the White House.
(Also see: White House Picks Engineer From Google to Fix Sites)
Smith will take over as chief technology officer from Todd Park, a former Silicon Valley executive, who has returned to California.
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