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High quality sodium vanadate (β-Na0.33V2O5) nanowires were grown directly on conducting silicon substrates by a facile chemical solution deposition method without employing catalyst, surfactant or carrier gas. The β-Na0.33V2O5 nanowires have typical average diameter of about 120 nm and length over 7 μm. The growth mechanism for β-Na0.33V2O5 nanowires are also proposed in detail. The electrical conductivity of β-Na0.33V2O5 nanowires measured along the growth direction was found to be about 0.57 S/cm. This is in good accordance with other results reported elsewhere. The field emission characteristics of β-Na0.33V2O5 nanowires were also investigated. It was found that high current density (550 μA/cm2) and low turn-on field voltage (0.6 V/μm) as well as high stability were obtained.