Planets residing in circumstellar habitable zones (CHZs) offer our best opportunities to test hypotheses of life's potential pervasiveness and complexity. Constraining the precise boundaries of habitability and its observational discriminants is critical to maximizing our chances at remote life detection with future instruments. Conventionally, calculations of the inner edge of the habitable zone (IHZ) have been performed using both 1D radiative-convective and 3D general circulation models. However, these models lack interactive three-dimensional chemistry and do not resolve the mesosphere and lower thermosphere (MLT) region of the upper atmosphere. Here we employ a 3D high-top chemistry-climate model (CCM) to simulate the atmospheres of synchronously-rotating planets orbiting at the inner edge of habitable zones of K-and M-dwarf stars (between T eff = 2600 K and 4000 K). Specifically, we present the first simultaneous 3D investigation of climate, photochemistry, and circulation on moist and runaway greenhouse atmospheres. Simulations are conducted for planets with N 2 -O 2 -H 2 O v -CO 2dominated atmospheres around a range of stellar spectral types with self-consistent stellar spectral energy distribution (SED)-orbital period relationships. While our IHZ climate predictions are in good agreement with GCM studies, we find noteworthy departures in simulated ozone and HO x photochemistry. For instance, climates around inactive stars do not typically enter the classical moist greenhouse regime even with high ( 10 −3 mol mol −1 ) stratospheric water vapor mixing ratios, which suggests that planets around inactive M-stars may only experience minor water-loss over geologically significant timescales. In addition, we find much thinner ozone layers on potentially habitable moist greenhouse atmospheres, as ozone experiences rapid destruction via reaction with hydrogen oxide radicals. Using our CCM results as inputs, our simulated transmission spectra and secondary eclipse thermal emission spectra show that both water vapor and ozone features of these atmospheres could be detectable by instruments NIRSpec and MIRI LRS aboard the James Webb Space Telescope. Our work indicates that simultaneous constraints on the UV emission of low-mass stars and the orbital properties of their attending planets, in conjunction with coupled physical-chemical numerical modeling, will be critical to understanding the habitability and observational prospects of rocky exoplanets.