Gibbsite (alpha-Al(OH)(3)) transformation into layered double hydroxides, such as lithium aluminum hydroxide dihydrate (LiAl-LDH), is generally thought to occur by solid-state intercalation of Li+, in part because of the intrinsic structural similarities in the quasi-2D octahedral Al3+ frameworks of these two materials. However, in caustic environments where gibbsite solubility is high relative to LiAl-LDH, a dissolution-reprecipitation pathway is conceptually enabled, proceeding via precipitation of tetrahedral (T-d) aluminate anions (Al(OH)(4)(-)) at concentrations held below 150 mM by rapid LiAl-LDH nucleation and growth. In this case, the relative importance of solid-state versus solution pathways is unknown because it requires in situ techniques that can distinguish Al3+ in solution and in the solid phase (gibbsite and LiAl-LDH), simultaneously. Here, we examine this transformation in partially deuterated LiOH solutions, using multinuclear, magic angle spinning, and high field nuclear magnetic resonance spectroscopy (Al-27 and Li-6 MAS NMR), with supporting X-ray diffraction and scanning electron microscopy. In situ Al-27 MAS NMR captured the emergence and decline of metastable aluminate ions, consistent with dissolution of gibbsite and formation of LiAl-LDH by precipitation. High field, ex situ Li-6 NMR of the the progressively reacted solids resolved an O-h Li+ resonance that narrowed during the transformation. This is likely due to increasing local order in LiAl-LDH, correlating well with observations in high field, ex situ Al-27 MAS NMR spectra, where a comparatively narrow LiAl-LDH O-h Al-27 resonance emerges upfield of gibbsite resonances. No intermediate pentahedral Al3+ is resolvable. Quantification of aluminate ion concentrations suggests a prominent role for the solution pathway in this system, a finding that could help improve strategies for manipulating Al3+ concentrations in complex caustic waste streams, such as those being proposed to treat the high-level nuclear waste stored at the U.S. Department of Energy's Hanford Nuclear Reservation in Washington State, USA.