Conventional approaches to flexible optoelectronic devices typically require depositing the active materials on external substrates. This is mostly due to the weak bonding between individual molecules or nanocrystals in the active materials, which prevents sustaining a freestanding thin film. Herein we demonstrate an ultrathin freestanding ZnO quantum dot (QD) active layer with nanocellulose structuring, and its corresponding device fabrication method to achieve substrate-free flexible optoelectronic devices. The ultrathin ZnO QD-nanocellulose composite is obtained by hydrogel transfer printing and solvent-exchange processes to overcome the water capillary force which is detrimental to achieving freestanding thin films. We achieved an active nanocellulose paper with ~550 nm thickness, and >91% transparency in the visible wavelength range. The film retains the photoconductive and photoluminescent properties of ZnO QDs and is applied towards substrate-free Schottky photodetector applications. The device has an overall thickness of ~670 nm, which is the thinnest freestanding optoelectronic device to date, to the best of our knowledge, and functions as a self-powered visible-blind ultraviolet photodetector. This platform can be readily applied to other nano materials as well as other optoelectronic device applications.