An organic/inorganic composite, (DODA)(9)EuW10O36.9H(2)O, can form a highly ordered self-organizing film with a layered structure and almost fully interdigitated alkyl chains at solid supports. EuW10O369- is deduced to be oriented in its self-organizing film, resulting in its polarized emission, which offers an accessible approach to fabricating the functional thin films containing polyoxometalates. (C) 2004 Elsevier Inc. All rights reserved.