Rubiales sensationally refused to resign in a press conference as Royal Spanish Football Federation president on Friday afternoon despite backlash over his behaviour at the Women's World Cup.
The RFEF chief had been expected to step down after kissing Spain star Jenni Hermoso after La Roja beat England on Sunday.
Hermoso told a live stream shortly after that it was something she 'did not want'.
After the media was briefed that Rubiales was set to resign and be replaced by Pedro Rocha, he told an extraordinary general assembly that he was going nowhere.
And Putellas, who came on as a second-half sub in the World Cup final, has broken her silence, tweeting: "This is unacceptable. It's over. With you teammate @Jennihermoso."
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Putellas is one of the biggest names in women's football, having won seven league titles with Barcelona, as well as three Champions League titles and the Ballon d'Or Feminin twice.
She is the first of Hermoso's international teammates to speak out on the matter as pressure continues to mount on Rubiales.
In an astonishing rant, Rubiales blamed 'fake feminism' for the response to his actions and called the backlash a 'social assassination'.
As well as kissing Hermoso on the lips, he also grabbed his crotch as Spain beat England in the company of Queen Letizia and her teenage daughter.
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Rubiales screams 'I will not resign' as Spain managers applaud rant about 'false feminism'
He said: "This is the body that elected me and the body to which I must give explanations.
"I want to thank everyone for the messages of support that you have sent me, there have been many messages that I have received.
"I'm ready to be vilified to defend my ideals. I don't deserve this manhunt I have been suffering.
"I want to apologise without reservations for everything that happened in the box, when in a moment of euphoria I grabbed that part of my body that you have already seen.
"Of course I have to apologise, to the Queen, and to everyone who has felt offended. I have been in countless boxes and I have never behaved like that."