In this study, we fabricated a resistive random access memory (ReRAM) of metal-insulator-metal structures using a hydrogen silsesquioxane (HSQ) film that was deposited by a low-cost solution process as a resistance switching (RS) layer. For post-deposition annealing (PDA) to improve the switching performance of HSQ-based ReRAMs, we applied high energy-efficient microwave irradiation (MWI). For comparison, ReRAMs with an as-deposited HSQ layer or a conventional thermally annealed (CTA) HSQ layer were also prepared. The RS characteristics, molecular structure modification of the HSQ layer, and reliability of the MWI-treated ReRAM were evaluated and compared with the as-deposited or CTA-treated devices. Typical bipolar RS (BRS) behavior was observed in all the fabricated HSQ-based ReRAM devices. In the low-voltage region of the high-resistance state (HRS) as well as the low-resistance state, current flows through the HSQ layer by an ohmic conduction mechanism. However, as the applied voltage increases in HRS, the current slope increases nonlinearly and follows the Poole-Frenkel conduction mechanism. The RS characteristics of the HSQ layer depend on the molecular structure, and when the PDA changes from a cage-like structure to a cross-linked network, memory characteristics are improved. In particular, the MWI-treated HSQ ReRAM has the largest memory window at the smallest operating power and demonstrated a stable endurance during the DC cycling test over 500 times and reliable retention at room (25 °C) and high (85 °C) temperatures for 10⁴ seconds.