Perfluoroalkyl isocyanate-derived monolayers were prepared on oxidized aluminum surfaces by chemical vapor deposition (CVD) of 1H,1H,2H,2H-perfluorodecyl isocyanate (CF3[CF2](7)CH2CH2N=C=O, i.e R-F-NCO). Two types of oxidized aluminum substrates were studied: electrochemically polished aluminum plates (Al-Al2O3) and AIM 201 that was treated with boiling water (Al-Bw(Al2O3)). X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) confirmed that this CVD method produces a monolayer with a thickness of similar to 1.2 nm on Al-Al2O3 through a carbamate linkage without discernible change in surface morphology. After monolayer deposition, hydrophilic Al-Al2O3 surfaces become hydrophobic. Advancing and receding water contact angles are theta(A)/theta(R) = 125 degrees/103 degrees. AFM indicates that Al-Bw(Al2O3), surfaces contain 10-15-nm-size pebble-like features. This is due to both chemical and physical erosion of the aluminum surface caused by the boiling water treatment. Due to the presence of these topographical features, the CVD of R-F-NCO on Al-Bw(Al2O3), induces superhydrophobicity (theta(A)/theta(R) = 167 degrees/165 degrees). Al-Al2O3 and Al-Bw(Al2O3) based "control surfaces" were prepared with the conventional mono- and trifunctional organosilanes, 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane (CF3[CF2](7)CH2CH2Si[CH3](2)Cl, R-F-SiMe2Cl) and 1H,1H,2H, 2H-perfluorodecyltrimethoxysilane (CF3[CF2](7)CH2CH2Si[OCH3](3), R-F-SiMe2Cl) for comparison. In the case of (RSi)-Si-F(OMe)(3), the theta(A)/theta(R) values for Al-Al2O3 and Al-BW(Al2O3) are 125 degrees/110 degrees and 170 degrees/167 degrees respectively. R-F-SiMe2Cl-treated aluminum surfaces are much less hydrophobic. The theta(A)/theta(R) values for Al-Al2O3 and Al-BW(Al2O3) are 107 degrees/69 degrees and 137 degrees/87 degrees, respectively. XPS analysis of surface coverage is consistent with the contact angle behavior and the water sensitivity. Stability of these three monolayers in water is in the order: R-F-Si(OMe)(3) > R-F-NCO >> R-F-SiMe2Cl.