Charity Care Expansion Act of 2014 - Amends the Internal Revenue Code to allow a physician a tax deduction equal to the amount such physician would have otherwise charged for charity medical care provided on a volunteer or pro bono basis through a pre-existing agreement between the physician and a health care clinic or other organization providing health care to underserved or low-income individuals. Imposes an overal limitation on such deduction equal to 10% of the physician's gross income derived from physicians' services (as defined by the Social Security Act) or $10,000 for physicians who do not have income derived from physicians' services.

Repeals the block grant program for preventive health and health services under the Public Health Service Act.