Carbazole-based self-assembled monolayers have received considerable attention as hole-selective layers (HSLs) in inverted perovskite solar cells. As an HSL, the electron-blocking capability is important and directly related to electron affinity (EA). Low-energy inverse photoelectron spectroscopy (LEIPS) is the most reliable method for EA measurement. However, the intense electron-impact-induced fluorescence from carbazole interferes with their measurement. By improving the photon detector, we were able to measure 2PACz and MeO-2PACz LEIPS spectra and determine their respective EAs of 1.72 and 1.48 eV. These small EA values ensure effective electron-blocking capability of HSLs regardless of the type of perovskite layer.