Au trisoctahedrons (TOHs) with sharp tips and high-index facets have exceptional properties for diverse applications, such as plasmon-enhanced spectroscopies, catalysis, sensing, and biomedicine. However, the synthesis of Au TOHs remains challenging, and most reported synthetic methods are time-consuming or involve complex steps, hindering the exploration of their potential applications. Herein, we present a facile and fast approach to prepare Au TOHs with high uniformity and good control over the final size and shape, all within less than 10 min of synthesis, for surface-enhanced Raman spectroscopy (SERS) and refractive index sensing. The size of the Au TOHs can be easily tailored over a wide range, from 39 to 268 nm, allowing a tuning of the plasmon resonance at wavelengths from visible to near-infrared regions. The exposed facets of the Au TOHs can also be varied by controlling the growth temperatures. The wide tunability of size and exposed facets of Au TOHs can greatly broaden the range of their applications. We have also encapsulated Au TOHs with zeolite imidazolate framework (ZIF-8), obtaining core-shell hybrid structures. With the ability to tune Au TOH size, we further assessed their SERS performances in function of their size by detecting 2-NaT in solution, exhibiting enhancement factors of the order of 10 with higher values when the LSPR is blue-shifted from the laser excitation wavelength. Au TOHs have been also compared for refractive index sensing applications against Au nanospheres, revealing Au TOHs as better candidates. Overall, this facile and fast method for synthesizing Au TOHs with tunable size and exposed facets simplifies the path toward the exploration of properties and applications of this highly symmetrical and high-index nanostructure.