VAT and customs duties are different types of taxes.
From 1 July 2021, AliExpress is required under the new EU e-Commerce VAT rules to collect VAT for orders at EUR 150 or less that are shipping from outside of EU to buyers located in EU at check-out. Such VAT collected orders shall be declared for customs with AliExpress IOSS number, and you will not be charged with VAT again.
Parcels with goods valued no more than EUR 150 can also enjoy customs duty exemption. Parcels with goods valued more than EUR 150 will be subject to VAT and customs duties as appropriate upon importation.