Catalytic conversion of lignin to value-added aromatic compounds is still an open challenge, since the selective cleavage of the linkages interconnecting the aromatic molecules, especially the β-O-4 ones, is not efficiently achieved yet. Herein, novel titania-based nanostructured materials were synthesized using low-power-low-frequency ultrasound that demonstrated high efficiency for the selective cleavage of Cα-Cβ bond of β-O-4 linkages of lignin-inspired model compounds. Going a step ahead, experiments of sonophotocatalytic valorization of 2-phenoxy-1-phenylethanol were contacted for the first time, where the exposure to ultrasound leading to better conversion and selectivity towards the desired products in the case of the novel ultrasound-synthesized nano-photocatalyst. Mechanistic insights showcased that photogenerated holes are the main active species in the catalytic process. In general, this research work provides a green, effective, and cost-effective approach for the selective and efficient catalytic lignin valorization.