It worked for me with magento 1.6.2.
The best solution is the creation of an extension, but I didn't take the time.
Also beware that with the next magento update the changes will be overwritten.
1) Add the red parts to \js\mage\adminhtml\wysiwyg\tiny_mce\setup.js
theme_advanced_buttons1 : magentoPlugins + 'magentowidget,bold,italic,underline,strikethrough,|,justifyleft,justifycenter,justifyright,justifyfull,|,styleselect,formatselect,fontselect,fontsizeselect',Add the spellchecker_languages (see lines above) according to you needs:
theme_advanced_buttons2 : 'cut,copy,paste,pastetext,pasteword,|,search,replace,|,bullist,numlist,|,outdent,indent,blockquote,|,undo,redo,|,link,unlink,anchor,image,cleanup,help,code,|,forecolor,backcolor',
theme_advanced_buttons3 : 'tablecontrols,|,hr,removeformat,visualaid,|,sub,sup,|,charmap,iespell,media,advhr,|,ltr,rtl,|,fullscreen,|,spellchecker',
theme_advanced_buttons4 : 'insertlayer,moveforward,movebackward,absolute,|,styleprops,|,cite,abbr,acronym,del,ins,attribs,|,visualchars,nonbreaking,pagebreak',
theme_advanced_toolbar_location : 'top',
theme_advanced_toolbar_align : 'left',
theme_advanced_statusbar_location : 'bottom',
theme_advanced_resizing : true,
convert_urls : false,
relative_urls : false,
content_css: this.config.content_css,
custom_popup_css: this.config.popup_css,
magentowidget_url: this.config.widget_window_url,
magentoPluginsOptions: magentoPluginsOptions,
spellchecker_languages : 'English=en,+Deutsch=de',
......
This enables you to specify what languages your pspell installation can handle. The value of this option should be a comma separated name value list in the following format name1=value1,name2=value,name3=value where name is the string to present in the menu and the value is a ISO language code like sv or en. If you add a + character infront of the name it will be the default value for the spellchecker. The default value for this option is: +English=en.
2) Go to http://www.tinymce.com/download/download.php and get the PHP Spellchecker.
3) Put the folder spellchecker from this zip inside \js\tiny_mce\plugins
That's all. Have fun.