Aluminum-doped ZnO (AZO) thin films with thin film metallic glass of Zr50Cu50 as buffer are prepared on glass substrates by the pulsed laser deposition. The influence of buffer thickness and substrate temperature on structural, optical, and electrical properties of AZO thin film are investigated. Increasing the thickness of buffer layer and substrate temperature can both promote the transformation of AZO from amorphous to crystalline structure, while they show (100) and (002) unique preferential orientations, respectively. After inserting Zr50Cu50 layer between the glass substrate and AZO film, the sheet resistance and visible transmittance decrease, but the infrared transmittance increases. With substrate temperature increasing from 25 °C to 520 °C, the sheet resistance of AZO(100 nm)/Zr50Cu50(4 nm) film first increases and then decreases, and the infrared transmittance is improved. The AZO(100 nm)/Zr50Cu50(4 nm) film deposited at a substrate temperature of 360 °C exhibits a low sheet resistance of 26.7 Ω/□, high transmittance of 82.1% in the visible light region, 81.6% in near-infrared region, and low surface roughness of 0.85 nm, which are useful properties for their potential applications in tandem solar cell and infrared technology.