Shalala, 58, was not hurt.
The incident occurred about 7:15 a.m. after she had withdrawn money from an ATM near her home in the Georgetown section of town and was walking back to her car, said Lt. Pat Burke of the District of Columbia Police.
A man tried to grab Shalala's wallet, telling her, "Give it up! Give it up!" Burke said.
"Ms. Shalala falls to the ground, curls into a fetal position and screams her lungs out," Burke said.
When a witness approached, the man and a woman standing nearby jumped into their car, joining a second woman already behind the wheel. The three then drove off.
Shalala noted the license plate and called police, who arrived quickly, Burke said.
Police said they apprehended the trio after witnesses reported seeing three people fleeing a car in another part of Georgetown.
The secretary was able to identify a man and one of the women when police brought them back to the crime scene, said Shalala's spokeswoman, Melissa Skolfield.
"She thinks the police did an excellent job," Skolfield said.
Burke credited Shalala with quick thinking in protecting herself and helping police make arrests.
"Ms. Shalala did what she felt was necessary to protect herself and it worked well for her." He said she was "very astute" in getting the license-plate number of the suspects and relaying it to police.
Police determined the vehicle was stolen and found items stolen from a young woman earlier Sunday.
Charged with attempted robbery, robbery and use of an unauthorized vehicle were district residents Tawana Nicole Clark, 20; Donald Sewell Clark, 22; and Sylvia Lorraine Dorsey, 20.