The incident took place around 5:30 a.m. Friday while police were attempting to serve a search warrant at a residence on Circle M Drive.
Four officers were hit by bullets, but two were protected by safety equipment. The other two were taken to Carl R. Darnall Army Medical Center and were then transferred to Scott & White.
One officer was in critical condition and the other was in good condition, police spokeswoman Carroll Smith said.
Marvin Louis Guy, of Killeen, was arrested and faces charges of three counts of attempted capital murder. He was being held in the Bell County Jail in lieu of $3 million bonds.
A 50-year-old woman was also arrested, though her name and any charges she may face weren't reported.
"The tragic events that unfolded have left the members of the Killeen Police Department and their families seeking answers to a senseless, destructive act," said Police Chief Dennis Baldwin.
"The families of the injured officers are aware of the outpouring of love, prayers, and support from the Central Texas Community. On behalf of the Killeen Police Department and the families of the injured officers, I would like to express our appreciation."