We report fabrication of a flexible, thorn-like ZnO-multiwalled carbon nanotube (MWCNT) hybrid paper with high aspect ratio for efficient ultraviolet (UV) sensing and photocatalyst applications. The thorn-like ZnO-MWCNT hybrid paper was synthesized via atomic layer deposition (ALD) of a uniform ZnO thin film on the outside surface of the MWCNT followed by hydrothermal growth of ZnO branches. The hybrid paper achieved very high surface to volume ratio, which is favorable for photodetector and photocatalyst applications. A photodetector fabricated from the hybrid paper demonstrates a high sensitivity to UV light with a maximum photoresponsivity of 45.1 A W⁻¹ at 375 nm, corresponding to an external quantum efficiency as high as 14927%. The rise time and fall time of the UV photodetector are 29 ms and 33 ms, respectively, indicating fast transient response characteristics for the device. The high photoresponsivity and fast transient response are attributed to efficient carrier transport and collection efficiency of the hybrid paper. Besides, the thorn-like ZnO-MWCNT hybrid paper demonstrates excellent photocatalytic performance under UV irradiation, enabling photo-degradation of organic dyes such as Rhodamine B (RhB) within 90 minutes, with good recyclability.