The shooting happened at an apartment in Pasadena near Fairmont shortly before 3:30 a.m. Monday.
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The man reportedly thought he heard a break-in at the door and grabbed his weapon. Investigators believe his live-in girlfriend was already inside the apartment when the shooting happened.
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Officials said the woman was shot several times and taken to Memorial Hermann by Life Flight, where she later died.
Investigators said there is damage to the door of the apartment, though it is unclear if the damage is old or new.
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"We're going to collect shell casings. We're going to look at the trajectory of the bullets and compare that to his statement and try to see if everything matches up. If it truly is accidental, obviously this is a very sad situation," Sgt. Raul Granados said. "If he did believe there was a break-in and, in fact, there wasn't, he ended up shooting his loved one. It's a very difficult situation for him. If there was an intruder, obviously, we want to find maybe doorbell cameras, maybe cameras at the apartment complex, to see if we are going to have to look for a suspect out there, or what happened at the door that startled him enough to get his weapon out and start shooting."
Police said the boyfriend stayed at the scene and is cooperating with investigators. He was being questioned about what exactly led up to the deadly shooting.