Lead halide perovskites (LHPs) have garnered considerable interest, owing to their advantageous optoelectronic properties and ease of synthesis. However, understanding their intricate structure-property relationships remains challenging, for both bulk and nanoscale forms, such as colloidal quantum dots (QDs). In this study, in addition to conventional characterization by X-ray diffraction and optical absorption, we show that variable temperature solid-state nuclear magnetic resonance spectroscopy, complemented by computational modeling, provides unique insight into the local coordination geometry and electronic structure of LHPs in relation to the moderate change in composition or materials morphology. For CsPbBr