The nanocrystal (NC) work-function engineering, which plays an important role on the NC memory characteristics such as memory window and retention time, were long regarded as a matter of choice on NC materials. In this letter, we report opposite polarities of charge storage in Au NC memories with different control oxides. The effective NC work function is found to be not only a bulk property of the NC, but also governed by the interface with surrounding dielectric, as a result of the Fermi-level pinning. By replacing Au NCs with C60 molecules, we also show the pinning effect generally exists at quantum-dot-based devices with high density of interface states. This fundamental interface property should be taken into account in the selection of NC and dielectric materials for the NC memory optimization