$re = '/(?(DEFINE)(?<urlPart>[^\\\\\s]+))\\\\\\\\(?&urlPart)\\\\(?&urlPart)\\\\\K(?&urlPart)/m';
$str = '### Positive matches
\\\\10.20.3.23\\S$\\COMPANY_NAME\\Main_5e08a942f39a430db0b081736a3f1881\\C_VOL-b002.spf
\\\\localhost\\part1\\selectMe
\\\\a\\b\\select-me but not me
\\\\a\\b\\select_me\\c\\d\\e.abc more text here
This is the link \\\\a\\b\\select-me\\c\\d\\e.abc inside a longer string
\\\\a\\b\\select_me_from_1st_link\\c.abc \\\\a\\b\\selectMeFrom2ndLink\\c.abc
## Negative matches
\\a\\b\\c\\dontSelectMe\\e\\f
\\\\\\\\dont-select-me or me
\\\\a \\b \\dont_select_me \\c \\d \\e.abc';
preg_match_all($re, $str, $matches, PREG_SET_ORDER, 0);
// Print the entire match result
var_dump($matches);
Please keep in mind that these code samples are automatically generated and are not guaranteed to work. If you find any syntax errors, feel free to submit a bug report. For a full regex reference for PHP, please visit: http://php.net/manual/en/ref.pcre.php