Both LiCO-coated nickel particles and fast firing technique were utilized in the manufacturing of MLCCs. They preserved the conductivity of Ni electrodes and provided the possibility of sintering the devices in oxidizing atmospheres. By using our method, the partial pressure of oxygen increased from 10 atm in conventional methods to 10 atm. The oxidizing atmosphere reduced the oxygen vacancy concentration as illustrated by the color change of the samples, and the results of EELS (electron energy loss spectroscopy). A systematic test with variable parameters, LiCO coating, the sintering schedule, and the oxygen flow during sintering were executed, and the dissipation factor and the capacitance of the MLCCs were documented. Three type of MLCCs were studied: Conventional (fired with the conventional technique), Uncoated (fast fired with uncoated Ni particles), and Coated (fast fired with the coated Ni particles). The maximum oxygen activity during sintering (i.e., pO = 1.2 × 10 atm) was obtained for coated samples, and due to the minimum V concentration, their dissipation factor decreased up to 60% relative to the Conventional ones. In addition, the impedance spectroscopy, together with the map of Li ion distribution, suggested that Li ions accumulated around the electrode-dielectric interface and amplified the activation energy at these interfaces. This eventually caused the coated MLCCs to show higher capacitance than their uncoated counterparts. As a conclusion, it is shown that the manufacturing process described in this paper can provide a better MLCC with higher capacitance, and lower dissipation factor and leakage current.