In light of the pressing environmental and health issues stemming from electromagnetic pollution, advanced electromagnetic wave absorbing materials are urgently sought to solve these problems. The present study delved into the fabrication of the resorcinol formaldehyde (RF)/SiO2 ceramic particles using the sol–gel route. From SEM images and XRD and XPS analysis, it can be seen that the RF/SiO2 ceramic particles are successfully generated after heat treatment at 1500 °C. At room temperature, the sample treated at 1500 °C exhibited a minimum reflection loss of −47.6 dB in the range of 2–18 GHz when the matching thickness was 5.5 mm, showcasing strong attenuation capabilities. Moreover, these particles demonstrated a considerable effective electromagnetic wave absorption bandwidth of 3.14 GHz, evidencing their potential for wideband electromagnetic wave absorption. The temperature adjustment played a pivotal role in achieving optimal impedance matching. When the heat treatment temperature is increased from 800 °C to 1500 °C, the dielectric properties of the material are improved, thus achieving the best impedance matching, thereby optimizing the material’s absorption properties for specific frequency ranges, which makes it possible to customize the electromagnetic wave-absorbing characteristics to meet specific requirements across a range of applications.