Let's decompile to see what GCC 4.8 does with it
Blagovest mentioned branch inversion to improve the pipeline, but do current compilers really do it? Let's find out!
Without __builtin_expect
#include "stdio.h"
#include "time.h"
int main() {
    /* Use time to prevent it from being optimized away. */
    int i = !time(NULL);
    if (i)
        puts("a");
    return 0;
}
Compile and decompile with GCC 4.8.2 x86_64 Linux:
gcc -c -O3 -std=gnu11 main.c
objdump -dr main.o
Output:
0000000000000000 <main>:
   0:       48 83 ec 08             sub    $0x8,%rsp
   4:       31 ff                   xor    %edi,%edi
   6:       e8 00 00 00 00          callq  b <main+0xb>
                    7: R_X86_64_PC32        time-0x4
   b:       48 85 c0                test   %rax,%rax
   e:       75 0a                   jne    1a <main+0x1a>
  10:       bf 00 00 00 00          mov    $0x0,%edi
                    11: R_X86_64_32 .rodata.str1.1
  15:       e8 00 00 00 00          callq  1a <main+0x1a>
                    16: R_X86_64_PC32       puts-0x4
  1a:       31 c0                   xor    %eax,%eax
  1c:       48 83 c4 08             add    $0x8,%rsp
  20:       c3                      retq
The instruction order in memory was unchanged: first the puts and then retq return.
With __builtin_expect
Now replace if (i) with:
if (__builtin_expect(i, 0))
and we get:
0000000000000000 <main>:
   0:       48 83 ec 08             sub    $0x8,%rsp
   4:       31 ff                   xor    %edi,%edi
   6:       e8 00 00 00 00          callq  b <main+0xb>
                    7: R_X86_64_PC32        time-0x4
   b:       48 85 c0                test   %rax,%rax
   e:       74 07                   je     17 <main+0x17>
  10:       31 c0                   xor    %eax,%eax
  12:       48 83 c4 08             add    $0x8,%rsp
  16:       c3                      retq
  17:       bf 00 00 00 00          mov    $0x0,%edi
                    18: R_X86_64_32 .rodata.str1.1
  1c:       e8 00 00 00 00          callq  21 <main+0x21>
                    1d: R_X86_64_PC32       puts-0x4
  21:       eb ed                   jmp    10 <main+0x10>
The puts was moved to the very end of the function, the retq return!
The new code is basically the same as:
int i = !time(NULL);
if (i)
    goto puts;
ret:
return 0;
puts:
puts("a");
goto ret;
This optimization was not done with -O0.
But good luck on writing an example that runs faster with __builtin_expect than without, CPUs are really smart those days. My naive attempts are here.
C++20 [[likely]] and [[unlikely]]
C++20 has standardized those C++ built-ins: How to use C++20's likely/unlikely attribute in if-else statement They will likely (a pun!) do the same thing.