An inorganic-organic hybrid 3-D Fe-III-Ce-III heterometallic antimonotungstate framework [Ce(H2O)(5) (2,6-pdca)](4)H-2[Fe-4(H2O)(6)- (SbW9O33)(2)]center dot 38H(2)O (1) (2,6-H(2)pdca = 2,6-pyridine-dicarboxylic acid) has been synthesized via a hydrothermal method by the one-pot reaction of 2,6-H(2)pdca, FeCl3 center dot 6H(2)O, Ce(NO3)(3)center dot 6H(2)O, and Na-9[B-alpha-SbW9O33]center dot 19.5H(2)O. Notably, the structural unit of 1 possesses a Krebs-type [Fe-4(H2O)(6)(2,6-pdca)(2)(SbW9O33)(2)](10-) subunit supported with four bridging [Ce(H2O)(5)(2,6-pdca)](+) moieties. It is worth highlighting that adjacent structural units are concatenated together through heterobimetallic bridges to construct a 3-D framework. Furthermore, cuboid nanocrystal 1' was prepared under mild hydrothermal conditions based on the electrostatic interaction between 1 and K+. The effects of concentration and time on the morphology of nanocrystal 1' were also studied. The cuboid nanocrystal 1' was used as a modified electrode material for simultaneous electrochemical detection of dopamine and acetaminophen. The 1'-modified glassy carbon electrode shows good selectivity and sensitivity for detecting dopamine and acetaminophen.