A series of composites have been fabricated by introducing ionic liquid (IL) (ship) into chromium terephthalate MIL-101 (bottle) by ship-in-bottle method (IL@MIL-101s), the resulting IL@MIL-101s are endowed to high water retention, which is essential to proton conducting on multiple energy-involved applications at the low relative humidity (RH). The humidifying IL can lower water loss and increase water uptake, and thus improves water retention properties of the composites aided by the mesoporous MIL-101 at low RH. The hydropenic proton transfer pathways are modeled inside MOF and between IL-MOF, diminishing energy barrier routes for proton hopping, and thus a promotive proton transfer is rendered via Grotthuss mechanism. Specially, the IL@MIL-101 (SIB-3) unfolds a high proton conductivity (sigma = 4.4 x 10(-2) S cm(-1)) at RH as low as similar to 23%, five orders of magnitude increase than that of parent MIL-101 (1.1 x 10(-7) S cm(-1)) at 323 K. Besides, IL@MIL-101s as fillers are incorporated into polymer blends to form hybrid membranes, appearing the relatively high proton conductivity (4.3 x 10(-3) S cm(-1)) under similar to 23% RH at 323 K. (C) 2020 Elsevier Inc. All rights reserved.