This shop we can really recommend. You will find it in Metrograd when you enter from the crossing of Khreshatyk and Shevchenko Boulevard. It is a very tiny shop but has a good selection of books in English of all kinds. They have study and teachers' books, guides and maps, books for children, sci-fi, bestsellers like John Grisham or Agatha Christie as well as the Russian classics collection or the world classics. At the same time, they have good supplies of newly published books and if you don't find the book you were looking for, in most cases you will be able to book it through Globe if you pay a small deposit. Globe also has some audio tapes and there is always the Sale stand with selceted titles for lower price. Importantly, they don't mind at all if you just come and look, the staff is helpful, pleasant and they speak English.
Baboon Book & Coffee Shop
On Khmelnytskogo Street 39b there is a cafe/restaurant with live music at weekends but it is full throughout the week. The main reason is that the venue's walls are covered with bookshelves and you are welcome to sit down for a coffee and take out a book and read. All the books are for sale of course. There is a special section with books in English and they also have videos. You can get cheap books in a separate room with used books and if you bring your books, you can get a voucher in return.
Litera which used to be called Bukva (both means Letter in Ukrainian/Russian) is on Tolstogo Strret 11, opposite the Shevchenko Park. They have a wide choice of Russian and Ukrainian books and a section of English, German and French books. Litera also has a good choice of dictionaries and study books. In the basement there is a small cafe where you can sit and relax with your latest purchase. There is a second Litera store also in the Globus Shopping Mall on Independence Square.