A flexible paper-structured catalyst (PSC) that can be applied to the anode of a solid oxide fuel cell (SOFC) was examined for its potential to enable direct internal reforming (DIR) operation. The catalytic activity of three types of Ni-loaded PSCs: (a) without the dispersion of support oxide particles in the fiber network (PSC-A), (b) with the dispersion of (Mg,Al)O derived from hydrotalcite (PSCB), and (c) with the dispersion of (Ce,Zr)O2-δ (PSCC), for dry reforming of CH4 was evaluated at operating temperatures of 650–800 °C. Among the PSCs, PSC-C exhibited the highest CH4 conversion with the lowest degradation rate. The electrochemical performance of an electrolyte-supported cell (ESC) was evaluated under the flow of simulated biogas at 750 °C for cases without and with the PSCs on the anode. The application of the PSCs improved the cell performance. In particular, PSC-C had a remarkably positive effect on stabilizing DIRSOFC operation fueled by biogas. •Direct internal reforming (DIR) SOFC fueled by biogas has been investigated.•Paper-structured catalyst (PSC) was examined for the application to DIRSOFC.•Coking-tolerant PSC for dry reforming was developed by the dispersion of (Ce,Zr)O2-δ.•On-paper synthesis of (Ce,Zr)O2δ contributed to its higher dispersion.•Performance of DIRSOFC was stabilized by applying the developed PSC on anode.