GNU/GCC Documentation:
The GCC documentation covers how to use the GCC compiler and associated tools.
AVR-libc Documentation:
In general, libc (the standard C library), is the source of many of the functions and features we associate with C/C++ which are not actually part of the core language structure. Examples include printf(), scanf(), file I/O, string manipulation, floating-point math, sorting algorithms, etc.
The AVR-libc documentation covers the libc customized for the AVR processor series. Some special functions have been added to help access internal and I/O features of AVR processors, while other functions, such as file I/O, have been removed because they aren't relevant for small embedded processors.