A self-described "political junkie," Alexander moved to Washington soon after graduating to work on the Hill. She began her D.C. career with famed message man and Sen. Charles Schumer (D-N.Y.) as deputy press secretary in October 2001.

She left his office in April 2002. After a stint as Press Secretary for a 2002 Nevada congressional race, Alexander began working as communications director for Rep. Adam Schiff (D-Calif.). She left that job in April 2004 to work on ex-House Minority Leader Dick Gephardt's (D-Mo.) presidential campaign as South Carolina press secretary. "I loved it," she told the National Journal of life on the trail.

In fact, Alexander enjoyed campaign life so much that she travelled with Terry McAuliffe, the chair of the Democratic National Committee, during the 2004 general election.

She briefly left government life to work as press secretary for the United Nations Foundation. But she returned to Capitol Hill in 2006 as Biden's Senate office press secretary. Alexander quickly rose in the ranks to communications director for Biden's personal office as well as his spokesman on the Senate Foreign Relations Committee, of which Biden was chair. She held both jobs simultaneously while taking night classes at Georgetown University Law Center.

The balancing act became increasingly difficult during Biden's vice presidential campaign. Though Alexander remained in Washington, she helped with communication strategies, especially after Biden won the election.

Alexander said she spent one Sunday in December studying for a law school final while also preparing Biden for the Sunday morning talk shows. "Biden has been absolutely wonderful to work with," Alexander told the Cleburne Times Review. "I wouldn't have been able to go to law school and work for him if it wasn't for his support."

Alexander was named press secretary for the incoming vice president in December 2008. She served there until May 2011.

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