In conclusion, we have developed a “cellulose spacer” strategy to assemble nanocellulose with the well-designed coumarin-based probe molecule to fabricate the fluorescent solid nanomaterials. The composite CFC membrane shows rapid sensing toward and excellent removal of mercury ions. Furthermore, the CFC membrane shows excellent cytocompatibility, due to the nontoxicity of the as-prepared green materials to cells. Thus, this work makes a dual-functional membrane for both sensing and mercury removal available via a simple and cost-effective approach. It will be promising to assemble fluorescence materials with any desired sensing and removal ability following the developed “cellulose spacer” strategy, since there are plenty of obtainable fluorophores and receptors. This approach will provide a wide range of applications for metal ion sensing and removal in water treatment.