I was going to have that be my entire comment here, but I figured this was easy enough to check - so I pulled php 5.5.7 source, and because of option parsing complexities strstr ends up being implemented in terms of php_memnstr, which is a macro for zend_memnstr, which in turn calls memchr and memcmp repeatedly in a loop. So, no, libc's strstr doesn't seem to be used.
I'm a little unsure whether or why this has to be so complex, but after a quick dip the water doesn't seem inviting enough for me to follow up.
For example, Boyer-Moore (http://en.wikipedia.org/wiki/Boyer-Moore_string_search_algor...) starts by looking at the end of the substring. If it finds a match, it searches earlier. If it does not find a match, it can skip ahead by several characters (possibly even the length of the substring, depending on how the match failed). How much to skip ahead is a bit complicated, but can be calculated in advance.
Consider searching for a substring consisting of 1000 'a's. Boyer-Moore starts by looking at the 1000th (1-indexed) character. If it's an 'a', it then walks back and checks the 999th, 998th etc. However, if it's not an 'a', it can immediately skip on to examine the 2000th character, i.e. only looking at 1 in every 1000 characters. As you can imagine, this can be very fast!
The Railgun implementation seems to be a combination of improved Boyer-Moore (Boyer-Moore-Horspool-Sunday) with Rabin-Karp (which uses hashing). My understanding is that these algorithms complement each other, so if you have an input string that is particularly inefficient with one algorithm, it automatically picks the other one.
Since many programs have string-searching in their innermost loops, spending some time optimizing this function can be worthwhile.
As another commentator pointed out, libc's strstr assumes NUL-terminated strings. Maybe php's doesn't? Which seems a bit odd to me in light of the explanation of PHP's genesis as having roots in C, but stranger things...
I'm not surprised at all that libc's strstr would be complex.
I didn't read every update of the code but it looks like it is written in c only. Critical code is usually implemented with the best algorithm and then converted/optimized manually to/in assembly.