Complex terrain features—in particular, environmental conditions, high population density and potential socio-economic damage—make the Trans-Mexican Volcanic Belt (TMVB) of particular interest regarding the study of deep convection and related severe weather. In this research, 10 years of Moderate-Resolution Imaging Spectroradiometer (MODIS) cloud observations are combined with Climate Hazards Group Infrared Precipitation with Station (CHIRPS) rainfall data to characterize the spatio-temporal distribution of deep convective clouds (DCCs) and their relationship to extreme precipitation. From monthly distributions, wet and dry phases are identified for cloud fraction, deep convective cloud frequency and convective precipitation. For both DCC and extreme precipitation events, the highest frequencies align just over the higher elevations of the TMVB. A clear relationship between DCCs and terrain features, indicating the important role of orography in the development of convective systems, is noticed. For three sub-regions, the observed distributions of deep convective cloud and extreme precipitation events are assessed in more detail. Each sub-region exhibits different local conditions, including terrain features, and are known to be influenced differently by emerging moisture fluxes from the Gulf of Mexico and the Pacific Ocean. The observed distinct spatio-temporal variabilities provide the first insights into the physical processes that control the convective development in the study area. A signal of the midsummer drought in Mexico (i.e., “canícula”) is recognized using MODIS monthly mean cloud observations.