Adrian Lubecki, 19, from Ipswich in Suffolk has been remanded in custody and will appear before magistrates tomorrow to face counts of supplying the drug and possession with intent to supply.
A 20-year-old man and a 26-year-old man from Ipswich were also arrested on suspicion of supplying the drugs but have been released on bail while police continue their investigation.
The arrest comes after the deaths of three men from Suffolk were linked to the rogue batch of pills, as well as a fourth man from Shropshire.
A fifth man was taken to hospital on New Year's Day and is making a recovery, Suffolk Police added.The first victim, 22-year-old Lithuanian factory worker Justas Ropas, who was also known as Justin, collapsed and died at his home in Ipswich on Christmas Eve.
Police are linking his death with that of Gediminas Kulokas, 24, also from Ipswich, who died on New Year's Day.They are investigating the possibility the pair's death is linked to that of John Hocking, a 20-year-old labourer from Rendlesham in Suffolk - who also died on New Year's Day.
The death of Daniel Bagnall, 27, from Telford in Shropshire - the only one outside of Suffolk - who died hours after Mr Hocking, is also believed to have been connected.
All are believed to have taken one or more of a deadly batch of triangular red pills embossed with the Superman 'S' logo.
Suffolk Police took the unprecedented move of offering an amnesty to anyone who handed in the tablets, in a desperate attempt to get them off the streets.
Officers said the drugs are similar to some found in the Netherlands which contained a very high amount of the substance PMMA.
This gives the pills a delayed effect and users often overdose accidentally because they think the drug is not working, leading to a fatal rise in body temperature.
Chief Inspector Steve Denham said: 'As well as it being illegal to sell and buy drugs, it can also be very dangerous as we have sadly seen with these tragic deaths.
'We would urge everyone not to be tempted to take illegal drugs - you don't know where they have come from, what they are made up of, or how your body will react to them.
'If you have been offered drugs in the Ipswich area over the past few weeks, in particular ecstasy, we'd urge you to contact us with any information so that we can find those responsible and remove these dangerous drugs from the streets.'
Meanwhile, Suffolk Police said a man arrested on suspicion of being drunk and disorderly in Ipswich town centre earlier today became unwell and told officers he had taken a 'Superman' pill.
He was taken to Ipswich Hospital but has since been discharged.
Chief Superintendent Jon Brighton said: 'It is concerning that we have another report of a member of the public requiring medical treatment after taking a pill of the same description already under investigation.
'I would like to re-emphasise the messages we have given out so far - if anyone is in possession of these distinctive looking pills, please do not take them or pass them on, please hand them in to police or one of the other agencies listed.
'Our number one priority is to remove these drugs from our communities and prevent any further harm.'
