Phase separation and transformation induced by electrochemical ion insertion are key processes in achieving efficient energy storage. Exploration of novel insertion electrode materials/reactions is particularly important to unravel the atomic/molecular-level mechanism and improve the electrochemical properties. Here, we report the unconventional phase separation of a cyanide-bridged coordination polymer, Eu[Fe(CN)(6)]center dot 4H(2)O, under electrochemical Na-ion insertion. Detailed structural analyses performed during the electrochemical reaction revealed that, in contrast to conventional electrochemical phase separation induced by the elastic interaction between nearest neighbors, the phase separation of NaxEu[Fe(CN)(6)]center dot 4H(2)O is due to a long-range interaction, namely, cooperative rotation ordering of hexacyanoferrates. Kolmogorov-Johnson-Mehl-Avrami analysis showed that the activation energy for the phase boundary migration in NaxEu[Fe(CN)(6)]center dot 4H(2)O is lower than that in other conventional electrode materials such as Li1-xFePO4.