What’s the best practice to set html attribute via PHP?

You always want to HTML-encode things inside HTML attributes, which you can do with htmlspecialchars:

<span title="<?php echo htmlspecialchars($variable); ?>">

You probably want to set the second parameter ($quote_style) to ENT_QUOTES.

The only potential risk is that $variable may already be encoded, so you may want to set the last parameter ($double_encode) to false.