Two men, aged 66 and 64 from Narellan Vale, also appeared in Sydney courts charged with attempting to traffic heroin.
The arrests were made after a seven-month surveillance investigation involving the Australian Federal Police (AFP), NSW Police, the NSW Crime Commission and Customs.
Crime Commission Commissioner Peter Singleton called it a "textbook" example of how to catch serious criminals.
"The Crime Commission's role was one essentially of intelligence analysis," he told reporters in Sydney.
"We've managed to identify persons of interest, intercept telephones and ultimately we were able to identify a shipping container containing illicit drugs."
The street value of the narcotics remains unclear.
The drugs travelled through a number of countries before arriving in Australia.
Police have not ruled out further arrests either in Australia or overseas in connection with the seizure.
AFP Sydney manager Brian McDonald said heroin seizures had been relatively rare in recent months and the high Aussie dollar may be playing a role in attracting smugglers.
"I think it would be fair to say that heroin has not been the drug of choice that we have seen," he added.
"... Certainly, I think the market in Australia does make us attractive to organised crime, to bring illicit drugs into this environment."
- AAP