Paine's announcement comes the week after he stood down as Australian Test captain because a sexting scandal with a former Cricket Tasmania staffer was made public.
Paine sent lewd messages to a woman on the eve of the 2017/18 Ashes series, but an investigation cleared him of any code of conduct breach when the matter was brought to Cricket Australia's attention in 2018.
With this in mind, there has been much debate since about whether Paine should have been appointed full-time captain after Steve Smith's ban following the ball tampering scandal in South Africa in 2018.
Paine skippered the final match of that infamous tour and remained in charge of the Test team until last Friday, when he quit in an emotional statement to the press.
Paine announced last week that although he was standing down as Test captain, he intended to remain available for selection for this summer's upcoming Ashes series, the first Test of which starts in Brisbane on December 8.
That now looks increasingly unlikely and the wicketkeeper's decision to step away from cricket opens the door for either Alex Carey or Josh Inglis to make their Test debut behind the stumps.
Paine's last game for Australia was against India at the Gabba in January. He does not play limited overs cricket for the national side, and watched on at home as Aaron Finch led the team to a win at the T20 World Cup in the UAE.
Speaking last week about his decision to resign as captain, Paine said: "Although exonerated (by CA and CT investigations), I deeply regretted this incident at the time, and still do today. I spoke to my wife and family at the time and am enormously grateful for their forgiveness and support.
"We thought this incident was behind us and that I could focus entirely on the team, as I have done for the last three or four years. However, I recently became aware that this private text exchange was going to become public.
"On reflection, my actions in 2017 do not meet the standard of an Australian cricket captain, or the wider community. I'm deeply sorry for the hurt and pain that I have caused to my wife, my family, and to the other party.
"I'm sorry for any damage that this does to the reputation of our sport. And I believe that it is the right decision for me to stand down as captain, effective immediately. I do not want this to become an unwelcome disruption to the team ahead of what is a huge Ashes series.
"To Australian cricket fans — I'm deeply sorry that my past behaviour has impacted our game on the eve of the Ashes. For the disappointment I have caused to fans and the entire cricket community, I apologise.
"I've been blessed with a wonderful, loving and supportive family, and it breaks my heart to know how much I've let them down. They have always stood by me, been my most loyal fans, and I'm indebted to them for their support.
"I will remain a committed member of the Australian cricket team, and look forward with anticipation to what is a huge Ashes tour."
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