The woman is injured and receiving medical treatment, but is likely to appear in the Alexandra District Court later today.
Emergency services were called to the accident at 2.16pm on State Highway 8, 19km north of Tarras in Central Otago.
While police has a clear picture of what occurred, they are still asking for witnesses to come forward regarding the driving behaviour of both groups involved prior to the crash.
Cromwell Police have had several people contact them today with information.
The female pillion passenger on the rear of one of the motorcycles remains in a critical condition in Dunedin Hospital.
Her name will not be released.
Alcohol is not suspected to be a factor in the crash.
Police staff, including the Police Serious Crash Investigator are continuing to work on the investigation.
Central Otago police sub area commander Senior Sergeant Ian Kerrisk said the two men were confirmed dead at the scene.
Fire, police and ambulance personnel from Central Otago and the Waitaki district attended the crash and the road was closed for several hours.