Microstructure and electric behaviors of La2/3Cu3Ti4O12 (LCTO) ceramics prepared by the sol-gel method (SG) and solid-state method (SS) have been systemically investigated. The results indicated that LCTO-SG ceramics sintered at 1105 degrees C for 15 h showed larger grain size, higher density, and especially higher dielectric constant up to about 0.9-1.6 x 10(4) at 10(2)similar to 10(5) Hz compared to LCTO-SS ceramics. The higher dielectric constant of the LCTO-SG ceramics might be due to the stronger internal barrier layer capacitor (IBLC) effect. More notably, compared with LCTO-SS ceramics, two kinds of dielectric anomalies, one conduction activation energy value and same activation energies for the conduction and relaxation process in LCTO-SS ceramics, the LCTO-SG ceramics showed three kinds of dielectric anomalies, two values of conduction activation energy, and decrease in conduction activation energy with increasing temperature. The activation energies for the conduction and relaxation process in LCTO-SG ceramics showed great difference below about 210 degrees C, suggesting that the mechanism of electrical conduction and dielectric relaxation seem to be different in LCTO-SG ceramics. These remarkable differences in electric behaviors of LCTO ceramics prepared by sol-gel and solid-state methods were firstly found and analyzed.