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Efficient white-light-emitting single-material sources are ideal for sustainable lighting applications. Though layered hybrid lead−halide perovskite materials have demonstrated attractive broadband white-light emission properties, they pose a serious long-term environmental and health risk as they contain lead (Pb 2+ ) and are readily soluble in water. Recently, lead-free halide double perovskite (HDP) materials with a generic formula A(I) 2 B′(III)B″(I)X 6 (where A and B are cations and X is a halide ion) have demonstrated whitelight emission with improved photoluminescence quantum yields (PLQYs). Here, we present a series of Bi 3+ /In 3+ mixed-cationic Cs 2 Bi 1−x In x AgCl 6 HDP solid solutions that span the indirect to direct band-gap modification which exhibit tailorable optical properties. Density functional theory (DFT) calculations indicate an indirect− direct band-gap crossover composition when x > 0.50. These HDP materials emit over the entire visible light spectrum, centered at 600 ± 30 nm with full-width at half maxima of ca. 200 nm upon ultraviolet light excitation and a maximum PLQY of 34 ± 4% for Cs 2 Bi 0.085 In 0.915 AgCl 6 . Short-range structural insight for these materials is crucial to unravel the unique atomic-level structural properties which are difficult to distinguish by diffraction-based techniques. Hence, we demonstrate the advantage of using solid-state nuclear magnetic resonance (NMR) spectroscopy to deconvolute the local structural environments of these mixed-cationic HDPs. Using ultrahigh-field (21.14 T) NMR spectroscopy of quadrupolar nuclei ( 115 In, 133 Cs, and 209 Bi), we show that there is a high degree of atomic-level B′(III)/B″(I) site ordering (i.e., no evidence of antisite defects). Furthermore, a combination of XRD, NMR, and DFT calculations was used to unravel the complete atomic-level random Bi 3+ /In 3+ cationic mixing in Cs 2 Bi 1−x In x AgCl 6 HDPs. Briefly, this work provides an advance in understanding the photophysical properties that correlate long-to short-range structural elucidation of these newly developed solid-state white-light emitting HDP materials.