We exploit ionization-parameter mapping (IPM) as a powerful tool to measure the optical depth of star-forming H II regions. Our simulations using the photoionization code CLOUDY and our new, SURFBRIGHT surface-brightness simulator demonstrate that this technique can directly diagnose most density-bounded, optically thin nebulae using spatially resolved emission-line data. We apply this method to the Large and Small Magellanic Clouds (LMC and SMC), using the data from the Magellanic Clouds Emission Line Survey. We generate new H II region catalogs based on photoionization criteria set by the observed ionization structure in the [S II]/[O III] ratio and H{alpha} surface brightness. The luminosity functions from these catalogs generally agree with those from H{alpha}-only surveys. We then use IPM to crudely classify all the nebulae into optically thick versus optically thin categories, yielding fundamental new insights into Lyman-continuum (LyC) radiation transfer.