If you're talking about a relational database, then your table structure should look like this (with some sample data included here):
User table:
UserId: 17
FirstName: Jim
Last Name: Smith
Book table:
BookId: 42
Name: Harry Potter
Booking table:
BookingId: 4
UserId: 17
BookId: 42
The booking table is your association between users and their books. When you store data here, you should only store the IDs of the other tables, and those columns in the booking table (UserId, BookId) should be foreign keys that point to the other tables.
When you need to display information, you should join the tables in a query and get back all of the information you need.
If you need to add another association, you simply add another row to the booking table. For example, if you have another user with an ID of 20, and another book with an ID of 75, then you would simply add this row to your booking table:
Booking table:
BookingId: 5
UserId: 20
BookId: 75
Some links to help:
Normalization
SQL Joins
Foreign Keys