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High-quality YBa₂Cu₃O_7-x (YBCO) thick films with thickness over 4.0μm were deposited by photo-assisted metal-organic chemical vapor deposition (PhA-MOCVD) technique with high growth rates. Microstructures of YBCO thick films have been systematically investigated by scanning electron microscopy, high-resolution transmission electron microscopy, and selected area electron diffraction techniques. The fabricated YBCO thick films are very dense and single-crystal like with no visible grain boundaries or voids. The high quality of the prepared YBCO thick films was confirmed further by the results of X-ray diffraction analyses and J_c measurements. Thus, these thick YBCO films prepared by PhA-MOCVD technique have promising application potential in fields such as coated conductors.