CLUW's National Office is located in Washington, DC and is directed by the National President. The National Staff consists of an Executive Director and a Labor/Women’s Rights Advocate.

Its governing body consists of a National Officers Council, composed of 22 women union leaders, and a National Executive Board (NEB) elected at CLUW's Biennial Convention.

CLUW's National President is Elise Bryant of the Labor Heritage Foundation.

The National Officers Council is representative of members from a diverse cross-section of unions within the organization and meets regularly upon call of the president.

The National Executive Board (NEB) includes members of the National Officers Council, State Presidents, State Vice Presidents, Chapter Presidents, Union Delegates and Chapter Delegates. Union and chapter delegates are elected in proportion to their membership in CLUW. Board meetings are held at least three times within the 2 year period between conventions. Educational conferences are usually held the day preceding each NEB meeting.

The NEB maintains General Committees in the following areas:

Leadership Development, Minority Issues/Affirmative Action, Organizing the Unorganized, Legislative/Political Action, Young Women Workers/Recruitment, Media and New Technologies, Work and Family Issues, Mature Women Workers, Women in the Global Community, Women’s Health and Wellness, Women in Non-Traditional Jobs, and Education. Standing Committees, separate from General Committees, are the following: Finance, Elections, Sergeant-at-Arms, and Archives and History.