Irina Sukhanova, 51, has been detained by police in Zaporizhia, south-eastern Ukraine, on suspicion of murder, according to law enforcement officials.
The carer wanted to stop the girl, named Alesya, from crying on her first trial day at the private nursery - after she was bitten by another child.
A horrific CCTV video shows her tying the pillow over the baby's face before trying to get her to sleep.
The terrified girl suffocated from her own vomit because her face was covered, say police.
She died from 'gastric obstruction of the respiratory tract'.
Instead of urgently calling an ambulance, Sukhanova is accused of seeking to wipe the CCTV records.
Police later restored the video evidence, it was reported.
At an extraordinary court room confrontation during Sukhanova's custody hearing the teacher is seen denying to Alesya's grief-stricken parents that she murdered the helpless girl.
'I did not kill your child,' she said in the showdown.
Father Eduard Gak, 24, asked in disbelief: 'Did not kill? I saw how you did not kill.'
The teacher replied: 'You will understand…'
Gak told her: 'Shut your mouth.'
'By phone she [Irina] assured me everything was good, and to look at testimonials about her.
'We really checked them.'
She said: 'How could she put the child asleep like this when she was vomiting?'
Her husband said: 'My wife came home at about 10 am…, and suddenly got a call saying "Your child is not breathing".'
He then rushed to the nursery and attempted artificial respiration on his daughter, to no avail, and then called an ambulance.
'She was only slightly warm,' he said.
'It doesn't fit into my head what happened. Can you imagine what I saw?
'My only one wish is to do the same to her, to take this pillow and... I can't say it another way.'
Sukhanova claimed: 'It was a special bolster for the child, so if she falls, she would not injure her neck. It was only to protect the child, nothing more.'
She was detained on suspicion of murder and is also under investigation for running an illegal nursery.
Lawyer for the parents Teymur Mamedov said: 'Before the arrival of detectives, she removed the surveillance camera recordings from the hard drives, and hid the (pillow).
'She undressed the child and tried to hide other traces of the crime.'
Senior police officer Oleh Hryhorov said: 'The seized video and investigations prove the involvement of the owner of an illegal nursery school in the commission of a particularly serious intentional crime.....murder of a minor.'
A full-scale criminal investigation is now underway into the incident on 29 May.
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