Solid oxide fuel cells (SOFCs) are being extensively researched for clean power generation from coal‐derived syngas. Some of the contaminants in syngas such as phosphine (PH3) may interact with the SOFC anode material, and degrade its electrochemical performance and material properties. In this paper, a modified Sagnac interferometry method is utilized to monitor the anode surface transient temperature as a function of applied current densities under hydrogen and simulated coal syngas. Moreover, the poisoning effects of PH3 contaminant on the SOFCs performance are investigated in dry and moist conditions. The experimental results indicate that the Ni‐cermet‐based SOFC anode is more susceptible to degradation due to PH3 in the presence of steam than under dry conditions. These experiments are valuable for the validation and the development of SOFC electrochemical models, and understanding the anode‐contaminant interaction.