The tuning of the molecular material work-function via strong coupling with vacuum electromagnetic fields is demonstrated. Kelvin probe microscopy extracts the surface potential (SP) changes of a photochromic molecular film on plasmonic hole arrays and inside Fabry-Perot cavities. Modulating the optical cavity resonance or the photochromic film effectively tunes the work-function, suggesting a new tool for tailoring material properties. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.