UI guidelines for Xfce are defined by this and a few other pages. These are guide lines provided to make the look and feel of native Xfce application be alike between applications.
Other UI definitions
Generally Xfce uses the guidelines found in GNOME Human Interface Guidelines 2.0. But as an addition to this, the following provide a check list of things needed to be considered when making an Xfce application more Xfce like.
This list is originally provided by Jannis Pohlmann, and it is meant as an inspiration and a place to start, so please anything that is missing, please feel free to add it.