Is the external formatted Mac OS Extended (Journaled) ? If so, yes.
A strong warning: If you're trying to edit the Library (that is, make albums, move photos around, keyword, make books or slideshows etc.) or edit individual photos in it via Wireless be very careful. Dropouts are a common fact of wireless networking, and should one occur while the app is writing to the database then your Library will be damaged. Simply, I would not do this with my Libraries.