The search for quantum spin liquids (QSL) and chemical
doping in
such materials to explore superconductivity have continuously attracted
intense interest. Here, we report the discovery of a potential QSL
candidate, pyrochlore-lattice β-NaYbO<sub>2</sub>. Colorless
and transparent NaYbO<sub>2</sub> single crystals, layered α-NaYbO<sub>2</sub> (∼250 μm on edge) and octahedral β-NaYbO<sub>2</sub> (∼50 μm on edge), were grown for the first time.
Synchrotron X-ray single-crystal diffraction unambiguously determined
that the newfound β-NaYbO<sub>2</sub> belongs to the three-dimensional
pyrochlore structure characterized by the <i>R</i>3̅<i>m</i> space group, corroborated by synchrotron X-ray and neutron
powder diffraction and pair distribution function. Magnetic measurements
revealed no long-range magnetic order or spin glass behavior down
to 0.4 K with a low boundary spin frustration factor of 17.5, suggesting
a potential QSL ground state. Under high magnetic fields, the potential
QSL state was broken and spins order. Our findings reveal that NaYbO<sub>2</sub> is a fertile playground for studying novel quantum states.