Surachet said police tracked down and arrested 41-year-old Natthawat Simbida, alias Keng the Golden Tongue, in Phetchabun's Nam Nao district on Tuesday.
The four other suspects were identified as Jintana Promnoi, 32, Kanong Imkhunthong, 44, Surapol Supcharoen, 46, and Benchawan Plaisuan, 52.
Surachet said police are now hunting for two other suspects, Sombat Fomthaisong, 44 and Utama Khunhong, 42.
Surachet said the gang was suspected of opening call centres to deceive Thais by operating in foreign countries. The gang operated from China, Malaysia, Philippines and Vietnam.
Surachet said Natthawat was an "idol" of call-centre scammers and got his alias because of his ability to persuade victims.