The reinforced ceramics, known as ceramic matrix composites (CMCs), is playing an important role in modern advanced industrial applications. However, the fabrication of CMCs with both high toughness and high stiffness, which are normally considered mutually exclusive, is still challenging. Here, we develop a gradient property SiOC composite film reinforced with nanoscale tungsten-based particles using a novel avenue of the integration of hybrid nanoparticles inkjet printing and selective laser sintering. Mechanical results of SiOC-WOx films exhibit the stiffness-toughness co-enhancement, including a twofold improvement in hardness and modulus, and an over 3.8-fold better fracture toughness performance than its matrix. Moreover, owing to the metal-to-ceramic gradient properties, the films exhibit interfacial bonding strengths up to 86.6 MPa and operate stably even at 1050 ℃. Characterization results show that the excellent mechanical and interfacial performance is attributed to the significant gradient composition and uniformly dispersed self-assembled nanoscale reinforcing particles. The success of SiOC-WOx CMC films demonstrates the potential to accelerate the discovery of revolutionary nanocomposites using hybrid nanoparticles and bottom-up additive manufacturing processes.