Make whitehouse.gov a place to connect the people with Obama
Much like barackobama.com and change.gov are places to connect with the campaign and the transition team, the CTO could make it a top priority to create a site that allows the executive branch to have a conversation with the country and constituents:
Allow commenting on high-profile issues, complete with proposals, moderated discussion forums, perhaps moderated chats.
Structured discussion about legislation on the president's desk: encourage the Senate and the House to interconnect with this process as well.
Expose the issues that the government's departments are working on: surface to the web not just the issues the president is working on, but also the smaller issues the agencies under the administration's control are dealing with.
Create a document repository: as much as possible, allow easy access for citizen journalists to look through governmental data without needing to file FOIA requests.
Encourage all executive branch political appointees to blog and interact with their fans: if every agency had its corner of a social network, there would be people from around the nation who would gather around these profile pages and interact with the agencies.
In general, build a new kind of a social network for government: one where the profiles are for people in governmental positions, and the people they serve.