Structural delamination of bulk layered metal–organic frameworks (MOFs) remains a great challenge, largely owing to a lack of general synthetic strategies. Here, we reported a simple solvent-free intercalation strategy for the delamination of rare-earth-based MOF (RE-MOF) with a topology structure of MIL-78 by tuning the chain length of quaternary ammonium salts. Four types of quaternary ammonium salts, involving tetraethylammonium bromide (TEAB), tetrapropylammonium bromide (TPAB), tetrabutylammonium bromide (TBAB), and hexadecyl trimethyl ammonium bromide (CTAB) were introduced to investigate their intercalation capabilities. It is evident in our case that the interruption/intercalation behavior of quaternary ammonium salts differs with their steric structures, and the chain-like CTAB can induce obvious delamination of MIL-78 crystals. Particularly, the CTAB-intercalated ultrathin Eu-based MIL-78 nanosheets exhibited unique selective photoelectrochemical sensing property toward trace amounts of Fe3+ ions in aqueous solution with a detection limit of 0.0899 μM at a signal-to-noise ratio of 3. These results demonstrated a green bottom-up strategy to obtain high-quality RE-MOF nanosheets for potential photocurrent response applications.