The arrested included the driver of the businessman who was allegedly looted at Kansbahal area of Sundargarh district on Sunday noon.
The arrests were made yesterday, the police said adding another person allegedly involved in the crime is absconding.
The driver was the first to be arrested and gave out deatils of the four others involved in the incident, the police said.
Efforts are on to arrest the absconding person, the police added.