Tran Duc Duy, 30, a key member of the ring, was caught in January last year carrying 31 kilograms of heroin in his truck in the northern province of Hoa Binh.
Duy fired his gun at the police officers but failing to flee the scene, authorities said.
Police then arrested 22 other traffickers and dealers of the ring, which allegedly had been run by Nguyen Thanh Tuan for years.
The ring reportedly trafficked a total of 445 kilos of heroin in a single year from 2014 to early 2015.
Tuan, the ring leader, is still at large.
Duy allegedly earned more than VND500 million (nearly US$22,500) from trafficking drugs to other northern cities and provinces. It is unclear where the ring had bought the drugs.
Vietnam is one of the toughest countries against drug crimes. If found guilty, Duy and the other members will likely face death sentence.