In this study, glass fiber (GF)/phenol formaldehyde resin (PF)/epoxy resin (EP) three-phase electrical insulating composites were fabricated by selective laser sintering (SLS) additive manufacturing technology and subsequent infiltration. In the three-phase composites, glass fibers modified by a silane coupling agent (KH-550) were used as reinforcements, phenol formaldehyde resin acted as the binder and matrix, and infiltrated epoxy resin was the filler. Mechanical and electrical properties such as tensile strength, bending strength, dielectric constant, electrical conductivity, and electric breakdown strength of the GF/PF/EP three-phase composite parts were investigated. The results indicated that after being infiltrated with EP, the bending strength and tensile strength of the GF/PF/EP composites increased by 30% and 42.8%, respectively. Moreover, the flexural strength and tensile strength of the GF/PF/EP composite increased with the increase of the glass fiber content. More importantly, the three-phase composites showed high electrical properties. Significant improvement in the dielectric constant, electric breakdown strength, and resistivity with the increase in the content of glass fiber was observed. This enables the prepared GF/PF/EP composites to form complex structural electrical insulation devices by SLS, which expands the materials and applications of additive manufacturing technology.