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The concept of polycentricity has gained significance in discussions on spatial development in Europe in recent years. This paper presents new evidence on polycentric city networks in Central-Eastern Europe based on selected results of the ESPON project POLYCE (Metropolisation and Polycentric Development in Central Europe). The authors discuss existing applications of the concept in the context of EU spatial policies and present an exploratory analysis of relational polycentricity focused on international networks of firms and research co-operation between seven capital cities in CentralEastern Europe (Vienna, Bratislava, Prague, Warsaw, Berlin, Budapest and Ljubljana). Analysis of networks of firms in the advanced producer service sector reveals strong ties between Budapest, Prague, Vienna and Warsaw, with Berlin being less connected but hosting firm subsidiaries of higher order. The investigations on research networks within EU Research Framework Programmes demonstrate that Berlin and Vienna play dominant roles in research co-operation within the region and are also well integrated in European scientific communities. There is no clear indication that inter-urban firm and research networks are influenced by travel times or ethnic ties between the cities, but the similar structures of firm and research relations suggest that different kinds of interactions, networks and co-operation between cities often go hand in hand with each other and are connected in some way.