In this study, it was found that macroporous hydrogels were formed when self-assembly of fluorenyl-9-methoxycarbonyl (Fmoc)-diphenylalanine (Phe-Phe) peptides was induced using glucono-δ-lactone (GdL) in apparently frozen samples. Formed cryogels exhibited a heterogeneous structure with pore walls of densely packed fibres of assembled dipeptides and pores in the range 10-100 μm. Hydrogels formed from the same composition above the freezing point exhibited a homogenous structure without any apparent porosity. The formed gels were characterised using microscopy techniques, CD-spectroscopy and stress sweeps. The cryogels exhibited less mechanical strength than the hydrogels that might be due to the heterogeneous structure of the former. It appeared that the self-assembled peptide both in the cryo- and hydrogel maintained the β-sheet structure commonly attributed to these.