$ser = 'a:2:{i:0;s:5:"héllö";i:1;s:5:"wörld";}'; // fails
$ser2 = 'a:2:{i:0;s:5:"hello";i:1;s:5:"world";}'; // works
$out = unserialize($ser);
$out2 = unserialize($ser2);
print_r($out);
print_r($out2);
echo "<hr>";

But why?
Should I encode before serialzing than? How?

I am using Javascript to write the serialized string to a hidden field, than PHP's $_POST
In JS I have something like:

function writeImgData() {
    var caption_arr = new Array();
    $('.album img').each(function(index) {
         caption_arr.push($(this).attr('alt'));
    });
    $("#hidden-field").attr("value", serializeArray(caption_arr));
};