Interfaces of heterogeneous solids, ranging from polycrystalline materials to composites, are frequently encountered in nanotechnology. Electron transport in these materials and across their interfaces critically depends on the energy barriers electrons encounter on their way. Because of electrode structural heterogeneity, the barriers may exhibit significant spatial variations resulting in a broad distribution of barrier heights and built-in potentials. Quantification of the distributed interface barriers represents a formidable experimental challenge since direct association of interface properties with those of an outer free surface is generally inaccurate. Here we present a methodology enabling quantification of electron barriers at interfaces of semiconductors and metals with insulators using the electric field-dependent internal photoemission (IPE) of electrons. It is shown that practically relevant interfaces may contain "patches" with differences in barrier height (or the effective work function) of up to 1 eV, which makes the electrode heterogeneity a crucial factor in designing electron devices suitable for low-voltage operation.