Yes you can. Here's a simple example of how to get the preference reference and execute custom code on a click event.
public class ActivityPreferences extends PreferenceActivity
{
protected void onCreate( Bundle savedInstanceState )
{
super.onCreate( savedInstanceState );
addPreferencesFromResource( R.xml.preferences );
Preference myPref = findPreference( "MY_PREF" );
myPref.setOnPreferenceClickListener( new OnPreferenceClickListener()
{
public boolean onPreferenceClick( Preference pref )
{
// Run your custom method
}
} );
}
}