In this paper, a new post-functionalized nano-platform of Tb3+@UiO-66-DPA had been synthesized and characterized by FTIR spectra, PXRD, SEM, TGA and XPS. With the multi-functionalized nano-platform of Tb3+@UiO-66-DPA, the selective detection and identification of two typical simulants (diethyl chlorophosphate, DCP, and 2-chloroethyl ethyl sulfide, CEES) of chemical warfare agents (nerve agents and mustard gas) had been realized. DCP sensitized and enhanced the ‘antenna effect’ of Tb3+@UiO-66-DPA through the inhibition of non-radiative deactivation vibrational energy transfer pathways, and the quantitative assay of CEES was achieved through the new Cu2+-mediated luminescent assay method. This study would provide a reliable and effective methodology to detect nerve agent and mustard gas simulants simultaneously via the excellent multi-functional lanthanide nano-materials platform.