Siloxane, a common contaminant present in biogas, is known for adverse effects on cogeneration prime movers. In this work, the solid oxide fuel cell (SOFC) nickel-yttria stabilized zirconia (Ni-YSZ) anode degradation due to poisoning by siloxane was investigated. For this purpose, experiments with different fuels, different deposition substrate materials, different structure of contamination siloxane (cyclic and linear) and entire failure process are conducted in this study. The electrochemical and material characterization methods, such as Electrochemical Impedance Spectroscopy (EIS), Scanning Electron Microscope- Wavelength Dispersive Spectrometers (SEM-WDS), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), and Raman spectroscopy, were applied to investigate the anode degradation behavior. The electrochemical characterization results show that the SOFCs performance degradation caused by siloxane contamination is irreversible under bio-syngas condition. An equivalent circuit model (ECM) is developed based on electrochemical characterization results. Based on the Distribution of Relaxation Time (DRT) method, the detailed microstructure parameter changes are evaluated corresponding to the ECM results. The results contradict the previously proposed siloxane degradation mechanism as the experimental results show that water can inhibit anode deactivation. For anode materials, Ni is considered a major factor in siloxane deposition reactions in Ni-YSZ anode. Based on the results of XPS, XRD and WDS analysis, an initial layer of carbon deposition develops and is considered a critical process for the siloxane deposition reaction. Based on the experimental results in this study and previous studies about siloxane deposition on metal oxides, the proposed siloxane deposition process occurs in stages consisting of the siloxane adsorption, initial carbon deposition, siloxane polymerization and amorphous silicon dioxide deposition.