Yes, as soon as you enter Slovenia via a toll section you are subject to paying the toll road fees. There is no exclusion. If you drive without a valid e-vignette you will be caught and heavily fined.
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Can I drive until the first exit on the motorway in Slovenia without a vignette?
Do I need an e-vignette if I only transit through Slovenia?
What happens if I drive without a Slovenian vignette?
How is the Slovenian vignette checked?
What different types of the Slovenian motorway e-vignette are available?