SiC-doped Yb2O3 structure (Yb2O3/SiC) was prepared to enhance the photocatalytic hydrogen evolution performance of Yb2O3 nanofiber, which have been performed by using catalyst in the presence of eosin-Y dye and triethanolamine, called photosensitizer and electron donor, respectively under solar light with/out cellulose and chitosan. In this study, cellulose and chitosan were used as biotemplates to increase the hydrogen production of Yb2O3/SiC nanofibrous catalyst in the photocatalytic hydrogen evolution reaction. Bioorganic-inorganic structures, cellulose-Yb2O3/SiC and chitosan-Yb2O3/SiC, were obtained by simply adding cellulose and chitosan to the reaction cell without any additional treatment. Cellulose and chitosan also used as a mediator for dispersion, hydrophilicity, morphological transformation and adhesion to semiconductor with the help of functional groups. The hydrogen production rate of bare SiC, bare Yb2O3, Yb2O3/SiC composite have been measured as 391 μmol g−1, 818 μmol g−1 and 1685 μmol g−1, respectively. Moreover, the hydrogen production rate of cellulose-Yb2O3/SiC and chitosan-Yb2O3/SiC composites were came up to 3346 μmol g−1, 4084 μmol g−1, respectively. These results have been showed that the Yb2O3/SiC nanofibrous catalyst showed higher activity in the presence of cellulose and chitosan. The existence of biopolymers will create a new field in photocatalytic hydrogen production studies with the advantages mentioned above, thanks to the functional groups.