In atmospheric conditions

Cu

I

is easily oxidized to Cu

II

due to the coexistence of moisture and oxygen. The poor oxidation inhibition of Cu

I

restricts the practical application of Cu

I

-containing materials. Herein we introduce an approach to construct a superhydrophobic microenvironment in Cu

I

-functionalized metal–organic frameworks by coordinatedly grafting organic amine compounds onto open metal sites (OMSs)

which can hinder the accessibility of moisture to pores thereby enhancing the stability of Cu

I

. As a proof of concept

MIL-101(Cr) with abundant OMSs and octadecylamine (OA) with long hydrophobic alkyl groups are used as carrier and surface coating. As superhydrophobic porous materials

the resultant Cu

I

M-OA exhibits improved Cu

I

stability in addition to retaining high crystallinity and intact porosity while almost all Cu

I

is oxidized in hydrophilic Cu

I

M upon exposure in a humid atmosphere for 30 h. Cu

I

M-OA owns excellent adsorption desulfurization performance (ADS) with regard to thiophene

benzothiophene

and 4

6-dimethyl dibenzothiophene. Even from

hydrated fuel

the adsorption performance of Cu

I

M-OA maintains well while the adsorption capacity of Cu

I

M decreases to 7% after 4 cycles. The remarkable moisture resistance

Cu

I

stability

and high porosity make the current adsorbent Cu

I

M-OA highly promising for the practical ADS process.