DelRio, who often worked with the DEA on drug investigations, spent several days on advanced life support after being shot twice while executing a search warrant Monday at 1454 Ruskin Avenue in Dayton.
The Dayton Police Department said on Wednesday that DelRio had sustained injuries that were "tragically not survivable."
Four suspects were later arrested they were identified as Courtney Allen, Lionel Combs III, Nathan Goddard Jr, and Cahke Courtner.
A funeral will be held next week. DelRio leaves behind a wife, five daughters, and 3 granddaughters.
An Ohio detective is in "grave condition" after being shot twice in the face while serving a drug-related search warrant, police said.
Jorge DelRio, a 30-year veteran of the Dayton Police Department, was shot a little before 7 p.m. Monday as he went down to the basement of a residence that was being searched by agents from the Drug Enforcement Administration, CNN reported.
He was rushed to a nearby hospital where he remains on "advanced life support," chief Richard Biehl said in a Tuesday news conference.
The recent shooting comes as the Dayton community is still recovering from an August shooting that left nine people dead and 27 injured. Patrol officers killed the shooter within 30 seconds after his first shot was fired.
"The extraordinary number and frequency of tragic events have fallen squarely on (the police department's) shoulders leaving little room for personal reflection, grieving or quite frankly, recovery," Dayton City Manager Shelley Dickstein said.
"While I am confident in their commitment and professionalism to get the job done, I remain concerned at the toll this year has taken," she said Tuesday.
Three men charged
Officers found four men inside the home and apprehended a juvenile who attempted to flee.
One of the men, 39-year-old Nathan S. Goddard Jr., faces a federal charge of assaulting a law enforcement officer engaged in a federal investigation with a deadly weapon, according to a news release from the US Attorney's Office of the Southern District of Ohio.
The warrant DelRio and DEA agents were serving came after a 3-month-long investigation into a fentanyl operation in the city, the attorney's office said.
The federal search warrant was issued as a result of that investigation, the office said.
In the home, officers recovered two loaded pistols with extended 30-round magazines, an AR pistol in a package loaded with 28 live rounds of ammunition, about 28 pounds of fentanyl and cocaine, more than 50 pounds of marijuana and more than $50,000 in cash, Biehl said Tuesday.
Goddard is also charged with conspiracy to possess with intent to distribute more than 400 grams of fentanyl, 500 grams or more of cocaine and marijuana, the US attorney's office said.
Two of the other men, Cahke Cortner, 39, and Lionel Combs III, 40, are also charged with conspiring to distribute the drugs, it said.
Goddard faces a maximum 30-year sentence for assaulting a federal office with a firearm, US Attorney for the Southern District of Ohio David M. DeVillers said in the news conference. The mandatory minimum for the narcotics conspiracy charge is 20 years and up to life in prison, he said.
The three defendants are scheduled for a hearing on November 8, the US attorney's office said.
CNN could not confirm attorneys for the three men.
'The shooting of this officer is an assault on this community'
DelRio joined the city's police department in 1989 and was sworn in as a DEA task force officer in May 2000, Biehl said.
"There's no doubt that through his hard work and dedication, Detective DelRio has saved and changed countless lives," the chief said. "Through his own sacrifice and peril, Jorge exemplifies the Dayton Police Department's motto: Honor through service and service with honor."
DelRio's work, Biehl said, had "impact regionally, nationally and internationally."
The shooting of DelRio was tragic and "uncalled for," Montgomery County Prosecutor Mat Heck, Jr., said.
"The shooting of this officer is an assault on this community," he said. "It's an assault on the justice system in this community."
Dayton Mayor Nan Whaley said the community already has "endured too much senseless tragedy this year, and the Dayton Police Department has risen to the task each time."
"In light of that, violence striking the department directly is especially painful," she said in a Facebook post.
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ABC News contributed to this article.