$re = '/(?:^| )[^@#\s_]*(_([^_\n]+)_)/m';
$str = 'Test sentence:
_some_val #ta_g_ and _some_ value, but some_val_ and #some_tag_value and @a_mention_ and a #_tag_
Should match (between underscores)
----
_italic text here_
police_woman_
_fire_fighter
a thousand _words_
_brunch_ on a Sunday
Should not match anything
----
@ta_g_
__value__
#some_tag_value
@some_value_here
@some_tag_
#some_val_
#_hello_
';
preg_match_all($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