From Tuesday people wishing to access the regime can make an initial application in a process that includes 70 safeguards.
Health Minister Chris Picton says no decisions about life and death are ever easy.
"But from today, eligible South Australians facing terminal illnesses and insufferable pain are entitled to choice and dignity at the end of life," he said.
"Because dying with dignity should be your choice."
South Australia's laws were passed in 2021 after 16 previous attempts to get legislation through state parliament over more than 25 years.
The assisted dying system includes a provision that people wishing to die must be resident in the state for at least 12 months.
A terminal diagnosis and a life expectancy of less than six months, or 12 months for a person with a neurodegenerative disease, must be confirmed for a patient to access the procedure.
The bill also requires patients to show they have decision-making capacity and are capable of informed consent, and to undergo an assessment by two independent medical practitioners.
They must have their request verified by independent witnesses and must be experiencing intolerable suffering that cannot be relieved.
Online training for doctors includes a competency assessment component and information about the eligibility of people seeking assistance as well as the assessment of any abuse or coercion.
A team of care navigators has been established with an interim nursing director to oversee four nursing and allied health staff, all with experience in end-of-life care.
A patient will be required to make three separate requests, including one in writing.
If all the requirements have been met, a final review is conducted before someone can apply for a permit to ensure the application complies with the safeguards set out in the legislation.
Once a permit is granted, the patient will be able to obtain medication for self-administration or in certain cases administration by a doctor.
Voluntary Assisted Dying South Australia said all those who had advocated for the legislation over many years were to be thanked, including those who had not lived to see the change.
"May there now be less suffering at the end of life and a more meaningful conversation around death," the organisation said.
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