Iron-based superconductivity develops near an antiferromagnetic order and out of a bad metal normal state, which has been interpreted as originating from a proximate Mott transition. Whether an actual Mott insulator can be realized in the phase diagram of the iron pnictides remains an open question. Here we use transport, transmission electron microscopy, X-ray absorption spectroscopy, and neutron scattering to demonstrate that NaFe$_{1-x}$Cu$_x$As near $xapprox 0.5$ exhibits real space Fe and Cu ordering, and are antiferromagnetic insulators with the insulating behavior persisting above the Neel temperature, indicative of a Mott insulator. Upon decreasing $x$ from $0.5$, the antiferromagnetic ordered moment continuously decreases, yielding to superconductivity around $x=0.05$. Our discovery of a Mott insulating state in NaFe$_{1-x}$Cu$_x$As thus makes it the only known Fe-based material in which superconductivity can be smoothly connected to the Mott insulating state, highlighting the important role of electron correlations in the high-$T_{rm c}$ superconductivity.
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