Most purchases have a built-in value added tax (IVA) of 20%. Non-E.U. (European Union) citizens are entitled to a refund of this tax if they spend more than 154.94€ (before tax) at any one store. To claim your refund, request an invoice from the cashier at the store and take it to the Customs office (dogana) at the airport to have it stamped before you leave. Note: If you're going to another E.U. country before flying home, have it stamped at the airport Customs office of the last E.U. country you'll be visiting (so if flying home via Britain, have your Italian invoices stamped in London).
Once back home, mail the stamped invoice back to the store within 90 days of the purchase, and they'll send you a refund check. Many shops are now part of the "Tax Free for Tourists" network. (Look for the sticker in the window.) Stores participating in this network issue a check along with your invoice at the time of purchase. After you have the invoice stamped at Customs, you can redeem the check for cash directly at the tax-free booth in the airport, or mail it back in the envelope provided within 60 days. For more info, check out www.globalrefund.com.