This paper describes that the performance of molecular diodes based on self-assembled monolayers (SAMs) depends on the type of anchoring group and purity of the precursors of these SAMs. The SAMs were formed on ultrasmooth template-stripped silver (AgTS) surfaces, which served as the bottom-electrode, and a eutectic alloy of gallium–indium was used as the top-electrode. When these junctions incorporate SAMs of the form S(CH2)11Fc (≡ SC11Fc) derived from HSC11Fc, they are good molecular diodes and rectify currents with rectification ratios R (≡ |J(−1.0 V)|/|J(+1.0 V)|) of ∼1.0 × 102. Replacing the thiol by disulfide or thioacetate functionalities in the precursor resulted in molecular diodes with values of R close to unity. Cyclic voltammetry and angle resolved X-ray photoelectron spectroscopy indicated that the SAMs derived from the disulfide or thioacetate precursors have lower surface coverages and are more defective than SAMs derived from thiols. In the junctions these defective SAMs caused defects and increased the leakage currents. The purity of the thiol-precursor is also crucial: 3 or 5% of disulfide present in the thiol caused a 28 or 61% decrease in R, respectively, and >15% of disulfide lowered R to unity, while the yield in nonshorting junctions remained unchanged. Our results show that the type of binding group, and the puritiy of the thiols, are crucial parameters in the experimental design of molecular electronic devices to ensure optimal device performance by keeping leakage currents to a minimum.