As a common building insulation material, foamed concrete has been widely used in engineering practice. However, the contradiction between compressive strength and thermal conductivity has become the main problem limiting the development and application of foamed concrete. Therefore, high-performance foam concrete (HPFC) with high compressive strength and low thermal conductivity was prepared by using graphene oxide (GO), fly ash, and polypropylene (PP) fiber as the main admixtures, and taking compressive strength, thermal conductivity, and microstructure as the main indices. Scanning electron microscopy, X-ray diffraction (XRD), and thermogravimetry–differential scanning calorimetry (TG-DSC) were employed to examine the mechanisms of HPFC. The results showed that when the content of fly ash was 25–35 wt%, PP fiber was 0.2–0.4 wt%, and GO was 0.02–0.03 wt%, the FC’s compressive strength increased by up to 38%, and its thermal conductivity reduced by up to 3.4%. Fly ash improved the FC’s performance mainly through filling, pozzolanic activity, and slurry fluidity. PP fiber enhanced the performance of FC mainly through bridging cracks and skeletal effects. The addition of GO had no significant impact on the type, quantity, or hydration reaction rate of the hydration products in these cement-based materials, and mainly improved the FC’s microstructural compactness through template action and crack resistance, thereby improving its performance.