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YBa2Cu4O8 has emerged as better choice in superconducting application thank to it strong thermal stability. High pressure techniques had been employed for the preparation of YBa2Cu4O8 but it might costly and/or inconvenient. Several research groups had showed that the YBa2Cu4O8 can also be prepared by conventional solid state method with heating at 1 atm oxygen pressure; however the phase formation processes are yet brief and clear. This work infiltrated the phase formation processes in preparing the YBa2Cu4O8 under solid state method with heating at 1 atm oxygen pressure. The effectiveness of the use of sodium nitrate as an enhancer was brought to light by the experiment results. Significant YBa2Cu4O8 phases were successfully synthesized.