A new octamolybdates based Cu‐organic polymer, [Cu2(mbix)2]2[Mo8O26] (mbix=1,3‐bis(imidazol‐1‐ylmethyl) benzene), abbreviated as Cu‐Mo8, was hydrothermally synthesized and characterized by routine method. Single‐crystal X‐ray diffraction analysis shows that {Mo8} as template and linker induce and promote the formation and connection of quadcore planetary loop (Cu4mbix4) to form the 2D planetary plane, then are stacked by van der Waals forces to stabilize the whole structure. Electrochemical results show that compound Cu‐Mo8 as electrode materials for supercapacitors exhibits the better supercapacitor performance of ca. 592.2 F g−1 at 1 A g−1, along with great cycling stability, which enriches POMs chemistry in the supercapacitor field.