Mechanoresponsive luminescent materials coupled with other functionalities are of particular interest due to their multiple external stimuli responsive properties. In this paper, a new sensitive mechanoresponsive luminescent coordination polymer, [Cd(INI)(DMF)2·DMF] (1) (H2INI = N-(5-isophthalic acid)-1,8-naphthalimide), has been successfully designed and synthesized. Complex 1 exhibits interesting mechanoresponsive and grinding-enhanced luminescence properties, and its luminescence colour changed from weak blue-green to bright blue upon grinding owing to the external pressure-induced destruction of ππ stacked arrangements in local defective areas. Moreover, the luminescence properties and uncoordinated carbonyl groups of well-ground g-1 endow it with excellent sensing ability for Cr3+ ions. This work will provide a new perspective to rationally design multifunctional coordination polymers that can serve as practical multi-responsive sensors to pressure and chemicals.