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There are some great bookstores in Santiago, but sadly books in Chile cost their weight in gold. The reason for this is the 19% VAT on books. There are various campaigns to scrap this tax, so hopefully things will improve because there are some lovely bookstores waiting to be explored.
Like the old saying with buses, in Santiago you won't see a bookstore for ages then suddenly you'll come across a bunch all together. This is the case on Avenida Providencia, especially in Galería Drugstore on the corner of Andrés de Fuenzalida.
Enter this mini-mall (named the Drugstore because the building used to be a pharmacy) and every second shop is a bookstore. There's Takk Libros, Donoso Libreria, Nueva Altamir, Feria Chilena del Libro and Ulises Libreria. Well stocked and great for browsing, you can find hardback coffee table books, novels, children's books, guide books, maps, calendars and gift cards.
Funnily, the mall is also full of ice cream shops (one of the best is Emporio de la Rosa where the chocolate ice cream is to die for) so you can stop for a few scoops between bookstores.