The plasma polymerization technique was used to surface modify glass fibers in order to form a strong but tough link between the glass fiber and the polyester matrix, and enable an efficient stress transfer from the polymer matrix to the fiber. Plasma polymer films of hexamethyldisiloxane, vinyltriethoxysilane, and tetravinylsilane in a mixture with oxygen gas were engineered as compatible interlayers for the glass fiber/polyester composite. The interlayers of controlled physico-chemical properties were tailored using the deposition conditions with regard to the elemental composition, chemical structure, and Young's modulus in order to improve adhesion bonding at the interlayer/glass and polyester/interlayer interfaces and tune the cross-linking of the plasma polymer. The optimized interlayer enabled a 6.5-fold increase of the short-beam strength compared to the untreated fibers. The short-beam strength of GF/polyester composite with the pp-TVS/O-2 interlayer was 32% higher than that with industrial sizing developed for fiber-reinforced composites with a polyester matrix.