Combined experimental and theoretical charge-density studies on free and metal-coordinated N-heterocyclic carbenes have been performed to investigate the extent of electron delocalization in these remarkable species. Tracing the orientation of the major axis of the bond ellipticity (the least negative curvature in the electron density distribution) along the complete bond paths distinguishes unambiguously between fully delocalized systems and those with interrupted cyclic electron delocalization. Evaluation of charge-density-based properties such as atomic quadrupole moments serves as a direct and quantitative measure of the extent of pi-electron delocalization and reveals consistency between theory and experiment. A detailed topological analysis of theoretical charge densities for two benchmark carbene systems, viz., 1,2-dimethylpyrazol-3-ylidene 1a and 1,3-dimethylimidazol-2-ylidene 2a, and their corresponding stable chromium pentacarbonyl complexes 1 and 2, highlights the advantages of charge-density-based criteria to analyze such complex electronic situations. Thus, la and 2a display a different extent of electron delocalization; yet nearly identical p, occupations at the carbene center are computed for la and 2a. However, atomic quadrupoles Q(zz) - the charge-density analogues of p, occupation - reveal faithfully the electronic differences in la and 2a and demonstrate the sensitivity of charge-density-based properties to the bonding situation. The acyclic aminocarbene (Pr2N)(2)CCr(CO)(4) has also been studied, and the high barrier to rotation about the C-N bond is shown not to arise solely from p(pi)-p(pi) bonding.