Vanadium dioxide (VO2) films with moth-eye nanostructures have been fabricated to enhance the thermochromic properties with different periodicity (d) to achieve antireflection (AR). It is revealed that the films with smaller d (210 and 440 nm) could increase both the luminous transmission (Tlum) and infrared transmission (TIR) at 25 and 90 (o)C, as the d is smaller than the given wavelength and the gradient refractive index produces antireflection. The average Tlum and TIR of VO2 increase with decreasing d. Compared with the planar film, the AR sample with periodicity of 210 nm and thickness of 140 nm can offer approximately 10% enhancement of Tlum and 24.5% increase in solar modulation (ΔTsol). With the addition of hydrophobic overcoat on the patterned VO2, ∼120° contact angle could be achieved. The present approach can tailor the optical transmittance in different wavelengths at high and low temperature together with self-cleaning, opening new avenues for producing hydrophobic VO2 with enhanced thermochromic properties for smart window applications.