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During geothermal energy development, the bottom high-temperature fluid continuously exchanges heat with the upper low-temperature wellbore and the stratum during its rising process. Thermal insulation cement (TIC) can increase the outlet temperature, thus effectively reducing the heat loss of the geothermal fluid and improving energy efficiency. In this study, vitrified microbubbles (VMB) were screened out by conducting an orthogonal test of compressive strength (CS) and thermal conductivity (TC) on three inorganic thermal insulation materials (VMB, expanded perlite (EP), and fly-ash cenosphere (FAC)). Fumed silica (FS) was introduced into the cement with VMBs, as its significant decreasing effect on the TC. Moreover, a cement reinforcing agent (RA) and calcium hydroxide [CH] were added to further improve the CS of TIC at 90 °C. The fresh properties, CS, TC, hydration products, pore-size distribution, and the microstructure of the cement were investigated. As a result, a TIC with a TC of 0.1905 W/(m·K) and CS of 5.85 MPa was developed. The main conclusions are as follows: (1) Increasing the mass fraction of the thermal insulation material (TIM) is an effective method to reduce TC. (2) The CH content was reduced, but the C–S–H gel increased as FS content increased due to the pozzolanic reaction of the FS. (3) As the C–S–H gel is the main product of both the hydration and pozzolanic reactions, the matrix of the cement containing 60% FS and VMBs was mainly composed of gel. (4) The 10% RA improved the cement fluidity and increased the CS of TIC from 3.5 MPa to 5.85 MPa by promoting hydration.

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