Reliability and durability are two major problems restricting for Solid oxide fuel cells (SOFCs) industrial applications. To ensure the long-term stability, understood the internal operation mechanism of SOFC was necessary. The polarization curve combined with the distribution of relaxation times (DRT) method to analyze the electrochemical impedance spectroscopy (EIS) was used to identify the SOFCs modulation and degradation effect through the excitation frequency. Dynamic evolution of carbon deposition process and specific time constants were determined employing EIS and DRT. Special attention was paid to the dependency between the complex reaction processes that occur during the different operation of SOFC. The corresponding frequencies of concentration and activation polarization resistances in EIS were investigated under various gas compositions. The high concentration polarization resistance caused by the addition of nitrogen and hydrogen starvation was the key limiting factor for high cell power density. The total polarization resistance increased from 1.50 Ω/cm2 to 5.26 Ω/cm2 when the H2:N2 ratio decreased from 1:0 to 1:5. The anode did not deteriorate due to the poisoning of Ni particles in a short-term tested under 0.5 A/cm2 current density when the fuel was methane.