Grandfather David Harris volunteers with the Yorkshire Ambulance Service and was transporting a patient from Keighley to the Royal Orthopaedic Hospital in Birmingham on July 6.
He returned on the same day – and the following day, he went online and paid the Clean Air Zone charge only to receive a Penalty Charge Notice (PCN) three weeks later.
The news comes after another driver, Corrinna Silver from Telford, had a similar problem which she said showed the system is “absolutely flawed”.
Mr Harris, who has three children and seven grandchildren, does not think there was an option to select a day when paying the charge for the visit in his Skoda Superb.
He and ended up paying the £8 charge again at a time when the council was still using “soft enforcement”.
Mr Harris, 73, a retired representative for a medical company and based in Leeds, said: “On July 6, I transported a patient from Yorkshire and went through the Clean Air Zone – I knew I had to pay for it.
“The following day, I put my registration and number in and paid my £8. It gave me a receipt and everything.
“Three weeks later I got a PCN to say I hadn’t paid my CAZ charge – bearing in mind the receipt I had on July 7.”
He said he went through the appeals process but ended up paying the charge again after not initially hearing anything back from the council.
He eventually received a response to say the second £8 payment had been accepted.
He said: “Their system is up the spout. I am wondering how many other people have had problems with this as well.”
He has claimed the one charge back from the ambulance service but has had to fund the second charge himself.
A Birmingham City Council spokesperson said the authority could not comment on individual cases.
But they said: “The council has always made clear its intention to take a fair and reasonable approach to the introduction of the Clean Air Zone. In the lead up and since the launch, we have made it very clear that the onus is on drivers to ensure that they pay any entry fees on time and on the correct dates.
“If a driver receives a PCN for not paying the Clean Air Zone daily fee they then have 28 days from the date of issue to submit a challenge through the online portal or in writing. The council takes every effort to respond as quickly as possible and, where possible, will take into account any other compelling reasons to cancel the PCN.
“We continue to encourage all drivers to check if their vehicle is subject to the daily fee and if it is to pay the fee within the 13 day payment window or consider more sustainable forms of transport, especially for shorter journeys.”
The Clean Air Zone has been introduced to tackle poor air quality in the city – responsible for an estimated 900 deaths per year.