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Glass fibers (GFs)/epoxy laminated composites always present weak interlaminar shear strength (ILSS) and low cross-plane thermal conductivity coefficient (λ⊥). In this work, silica-sol, synthesized from tetraethyl orthosilicate (TEOS) and KH-560 via sol-gel method, was employed to functionalize the surface of GFs (Si-GFs). Together with a spherical boron nitride (BNN-30), the thermally conductive BNN-30/Si-GFs/epoxy laminated composites were then fabricated. Results demonstrate that Si-sol is beneficial to the improvement of mechanical properties for epoxy laminated composites (especially for ILSS). The BNN-30/Si-GFs/epoxy laminated composites with 15 wt% BNN-30 fillers display the optimal comprehensive properties. In-plane λ(λ//) and λ⊥ reach the maximum of 2.37 and 1.07 W·m−1·K−1, 146.9% and 132.6% higher than those of Si-GFs/epoxy laminated composites (λ// = 0.96 W·m−1·K−1 and λ⊥ = 0.46 W·m−1·K−1), respectively, and also about 10.8 and 4.9 times those of pure epoxy resin (λ// = λ⊥ 0.22 W·m−1·K−1). And the heat-resistance index (THRI), dielectric constant (ε), dielectric loss (tanδ), breakdown strength (E0), surface resistivity (ρs) as well as volume resistivity (ρv) are 197.3 °C, 4.95, 0.0046, 22.3 kV·mm−1, 1.8 × 1014Ω, and 2.1 × 1014Ω·cm, respectively. [ABSTRACT FROM AUTHOR]