An organic/inorganic composite,(DODA) 9EuW10O36· 9H2O, 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.