Recently, the Ruddlesden-Popper bilayer nickelate La 3 Ni 2 O 7 has emerged as a superconductor with a transition temperature (T c ) of ~80 K above 14 GPa1-3. Achieving higher T c in nickelate superconductors, along with the synthesis of reproducible high-quality single crystals without relying on high oxygen-pressure growth conditions, remains a significant challenge4-7. Here we report superconductivity up to 96 K under high pressure in bilayer nickelate single crystals synthesized at ambient pressure. Energy dispersive spectroscopy, single-crystal X-ray diffraction, nuclear quadrupole resonance, and scanning transmission electron microscopy evidenced high homogeneity and crystal quality of the flux-grown La 2 SmNi 2 O 7-δ single crystals. La 2 SmNi 2 O 7 exhibits clear bulk superconductivity, including zero resistivity (T c,max onset = 92 K and T c,max zero = 73 K at 21 GPa) and Meissner effect (T c = 60 K at 20.6 GPa). Low-temperature high-pressure structural study indicates that both monoclinic and tetragonal structures can support superconductivity in this bilayer nickelate. Furthermore, we established a correlation between higher T c under high pressures and larger in-plane lattice distortion at ambient conditions, corroborated by observing even higher T c onset of 96 K in La 1.57 Sm 1.43 Ni 2 O 7-δ . This study overcomes key limitations in nickelate superconductor crystal growth, resolves the crystal structure in the superconducting state, and demonstrates an effective pathway towards achieving higher T c .