Photocatalytic conversion of benzyl alcohol (BA) into value-added fine chemicals and hydrogen (H2) in water medium provides a novel strategy for green synthesis. The construction of Z-scheme heterostructures not only realize enhanced charge-separation efficiency, but also remain strong drive force for photocatalytic reaction, which exhibit great potentials toward simultaneously generating benzaldehyde (BAD) and H2. Herein, we report a noble-metal-free Z-scheme photocatalytic system consisting poly(dibenzothiophene-S,S-dioxide) (PSO) and α-Fe2O3 for selective oxidation of BA with synchronous H2 production. Such nanocomposites can effectively transfer and reduce the recombination of photoexcited charge carriers, therefore maintaining the oxidizability of holes of α-Fe2O3 and the reducibility of electrons of PSO. As expected, PSO-Fe2O3 with a mass of ∼5 mg under optimal composition ratio exhibited an impressive photocatalytic activity with BAD and H2 yields up to 23.1 and 29.5 μmol h−1, respectively, which is among the top photocatalytic performance reported so far for selective photocatalytic oxidation of BA in the aqueous solution.