Core-level and valence-band x-ray photoemission spectra measured for molecular-beam-epitaxy-grown LaCrO(3)/SrTiO(3)(001) yield band offsets and potential gradients within the LaCrO(3) sufficient to trigger an electronic reconstruction to alleviate the polarity mismatch. Yet, the interface is insulating. Based on first principles calculations, we attribute this unexpected result to interfacial cation mixing combined with charge redistribution within CrO(2) layers, enabled by low-lying d states within LaCrO(3), which suppresses an electronic reconstruction.