Hybrid lead perovskites containing a mixture of organic and inorganic cations and anions have led to solar cell devices with performance and stability that are better than those of their single-halide analogs. 207Pb solid-state nuclear magnetic resonance and single-particle photoluminescence spectroscopies show that the structure and composition of mixed-halide and likely other hybrid lead perovskites are much more complex than previously thought and are highly dependent on their synthesis. While a majority of reports in the area focus on the construction of photovoltaic devices, this Perspective focuses instead on achieving a better understanding of the fundamental chemistry and photophysics of these materials, because this will aid not only in constructing improved devices but also in generating new uses for these unique materials.