The rules would "slow down the development, production and use" of synthetic fuels designed to substitute for petrol or diesel "at the expense of climate change", Classic Tankstellen said in a joint press release with its co-complainants.
Together the group filed an objection with the European court in Luxembourg in July.
The technology behind synthetic fuels, still under development, consists of producing fuels from CO2 using low-carbon electricity.
Advocates say this means the fossil fuel substitute is not a net producer of emissions over its lifetime, but environmental groups have objected to the idea, which is deemed too expensive and energy-intensive.
The ban on combustion engine cars is a critical part of the EU's push to be climate-neutral by 2050, with net-zero greenhouse gas emissions.
The stop was agreed by EU member states in March, after automotive powerhouse Germany held up approval to negotiate an exemption for synthetic fuels.
The legislation was unblocked after the European Commission agreed to work on a separate proposal to potentially allow the use of synthetic fuels, set to be approved by autumn 2024.
For the time being, the original text of the ban remains in place, prompting the legal complaint from German companies.
The group takes particular issue with the new regulations' focus on tailpipe emissions, rather than the environmental impact of the car as a whole.
"CO2-neutral fuels offer the only way to include combustion engine vehicles, which will continue to represent a predominant part of the vehicle fleet in the long term, in climate protection efforts," said Lorenz Kiene, CEO of Classic Tankstellen.
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