You cannot redeclare any functions in PHP. You can, however, override them. Check out overriding functions as well as renaming functions in order to save the function you're overriding if you want.
So, keep in mind that when you override a function, you lose it. You may want to consider keeping it, but in a different name. Just saying.
Also, if these are functions in classes that you're wanting to override, you would just need to create a subclass and redeclare the function in your class without having to do rename_function and override_function.
Example:
rename_function('mysql_connect', 'original_mysql_connect' );
override_function('mysql_connect', '$a,$b', 'echo "DOING MY FUNCTION INSTEAD"; return $a * $b;');