Yes, as long as you make a European shipment that applies VAT. It can be national (except the Canary Islands, Ceuta and Melilla) or within the European Union.
You can download your invoice by clicking on "Configuration", where you will find your shipment list. Then click on "Billing" and "My invoices". In this section you will be able to view and download your invoices
Remember that if you have used a VIES VAT number, VAT will not apply to intra-community transactions; more information can be found at VIES: What is it an how do I register?