We report a 2D layered metal-organic framework (MOF) with wide channels named NUS-1 and its activated analogue NUS-la composed of Zn4O-like secondary building units and tetraphenylethene (TPE)-based ligand 4,4'-(2,2-diphenylethene-1,1-diyl)dibenzoic acid. Due to its special structure, NUS-la exhibits unprecedented gas sorption behavior, glass-transition-like phase transition under cryogenic conditions, and responsive turn-on fluorescence to various volatile organic compounds. Our approach using angular ligand containing partially fixed TPE units paves a way toward highly porous MOFs with fluorescence turn-on response that will find wide applications in chemical sensing.