Advancing quantum information, communication and sensing relies on the generation and control of quantum correlations in complementary degrees of freedom. Here, we demonstrate the preparation of electron-photon pair states using the phase-matched interaction of free electrons with the evanescent vacuum field of a photonic-chip-based optical microresonator. Spontaneous inelastic scattering produces intracavity photons coincident with energy-shifted electrons. Harnessing these pairs for correlationenhanced imaging, we achieve a two-orders of magnitude contrast improvement in cavity-mode mapping by coincidence-gated electron spectroscopy. This parametric pair-state preparation will underpin the future development of freeelectron quantum optics, providing a pathway to quantum-enhanced imaging, electron-photon entanglement, and heralded single-electron and Fock-state photon sources.