Modified hollow glass microsphere (HGM) particles have been prepared by surface treatment. Coupling agents such as γ‐aminopropyltriethoxysilane (APTES), di(dioctylpyrophosphato) ethylene titanate (NDZ‐311), and glutaraldehyde (GA) were used as modifiers to improve the hydrophobicity of HGM. Compared with pristine HGM, the modified HGM, especially the particles coupled with APTES‐GA, show better properties on flexural strength, fracture toughness, and dynamic mechanical properties of phenolic syntactic foams. It is revealed that the coupling agent coating layer grafted onto the surface of HGM reduces the polarity of particles, avoiding agglomeration of HGM in phenolic matrix and exhibiting good interfacial interaction between HGM and phenolic matrix. The remarkable improvement of interfacial adhesion between APTES‐GA modified HGM and phenolic matrix is mainly due to the covalent linkage with phenolic resin while the physical entanglement of molecular chains dominates the linkage between other modified HGM and phenolic matrix. APTES‐GA treatment is a more appropriate surface modification method for inorganic particle reinforced phenolic matrix composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44415.