Neil Mellor joins the GLA on part-time secondment from BT, where he holds the position of head of policy and innovation in the telecoms firm's step-change e-government programme.
Over the next six months, Mellor will work with the GLA to build a prominent role for e-business in policy.
He will report to John Ross, Livingstone's senior economic policy adviser.
"The key thing is to ensure that there is a joined-up approach in all policy issues as far as e-business and e-governance is concerned. We have to make sure that the e-agenda is taken advantage of in all of these areas," he said.
At the top of the list of priorities is addressing education and training needs, and ensuring e-business provision issues are considered in future construction projects.
"It's important to understand what applications will best serve both business and citizens, such as flexible working, which could have a significant impact on the productivity and sustainability of the capital," Mellor said.
"But it's not about technology - it's about change and enabling people to get the biggest benefits from what that can offer."
Mellor replaces Colin Jenkins, formerly a special projects director at telecoms giant Energis, who held the position for nine months and is retiring.