Plasma-sprayed ceramic coatings are widely used to enhance the wear resistance of metallic substrates. However, the lamellar structure features of the coatings greatly degrade their wear resistance. In this work, a novel dense Na2Ti6O13 (NTO) coating with lamellae fully bonded was deposited using traditional atmospheric plasma spray. The microstructure and mechanical properties of NTO coating were characterized in comparison with that of TiO2 coatings with traditional lamellar microstructure and sintered-bulk-like microstructure deposited at different deposition temperatures. The fracture strength, microhardness, and fracture toughness of the coatings were tested. The sliding wear performance of the coatings was evaluated against the Si3N4 counterpart. Results showed that the as-sprayed NTO coating deposited at room temperature presented a sintered-bulk-like microstructure with sufficient interlamellar bonding, a low porosity of less than 1%, hardness of 785 Hv0.3, and fracture strength of 5808 MPa comparable to its sintered counterpart. It was found that the specific wear rate of ceramic coatings presents a significant load effect. The transition from mild wear to severe wear was observed for all coatings with the increase of wear load. The critical load for wear mechanism transition is highly dependent on the interlamellar bonding quality and fracture toughness of the coating. The deposition of the ceramic coatings with fully bonded splats increases the critical load by 1.5 times of the coating with the traditional lamellar structure. In the mild wear regime, the wear rate of NTO coating (0.5 × 10−6 mm3/Nm) is 5-10 times lower than that of traditional TiO2 coating (5.3 × 10−6 mm3/Nm), while even in severe wear regime, the wear rate of NTO coating is less than half of traditional TiO2 coating. The plastic deformation and microcutting are responsible for wear in mild wear regime, and lateral cracking in severe regime leading to significantly increased wear rate. The high wear resistance of NTO coating can attributed to its sintered-bulk-like microstructure and high toughness. Therefore, the NTO is a promising ceramic coating material of potential excellent wear performance.