We observed the thermochromism of the deeply colored zirconocene complex of 1,4-diphenyl-1,3-butadiene (DPBD) in the solid state. Variable-temperature C-13-CP/MAS NMR spectroscopy revealed that a remarkable change of the electronic structure of the DPBD molecule by constructing the complex propagates all over the carbon sites and that the distortion of the electronic structure of the complex becomes continuously large as temperature is decreased. This phenomenon is closely related to the thermochromism. The mechanism of the temperature variation of the electronic structure of the complex was attributed to the dynamics of phenyl ring and cyclopentadienyl ring of the complex. Fast rotation of the cyclopentadienyl ring around its fivefold axis with the extremely small activation energy of 28 meV (=2.6 kJ/mol) and 180 degrees flip rotation of the phenyl ring about the C-C bond with the activation energy of 84 meV (=7.7 kJ/mol) were recognized by the measurement of the spin-lattice relaxation rate of proton NMR. Semiempirical ZINDO molecular orbital calculation revealed that the deep color of the complex originates in the HOMO-LUMO and HOMO-LUMO+1 transitions. These molecular orbitals are sensitive to the orientation of the pi-orbital of cyclopentadienyl rings, suggesting that the dynamic perturbation is operative for the transition energies.