Three-dimensional (3D) architectures of YBO3/Eu3+ with different morphologies such as nest-like, rose-like, cruller-like, and flower-like, were hydrothermally synthesized by simply adjusting the ratios of surfactant polyethylene glycol-6000 (PEG-6000) to octadecylamine (ODA). These 3D architectures were all self-assembled by nanoflakes. X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FE-SEM), and photoluminescence (PL) spectra were used to characterize the morphology and structures of the samples. PEG-6000, ODA, and the ODA/PEG ratio played important roles in the formation process of various architectures. Rose-like architecture was chosen as a candidate, and the formation mechanism of the architecture was proposed on the basis of XRD analysis and SEM observation of the products at different reaction periods of time. As-synthesized samples displayed strong emission located at 591, 6 10, and 615 nm. Water contact angle measurements indicated that the films fabricated by the samples obtained under the different ratios of PEG-6000/ODA could exhibit tunable wettability ranging from superhydrophilicity to superhydrophobicity. This kind of one-pot bisurfactant-controlled hydrothermal synthesis method reported here provides a new strategy to realize the surfaces of functional materials with tunable wettability.