It is proposed that primary nucleation of amorphous microspherulites of hydrated silica in natural proto-precious-opal can be followed by a long range superlattice ordering process by means of electrostatic self-assembly. Necessary conditions in the thermodynamics are a high surface charge density on microspherulite surfaces, a long Debye length and an appropriate number density of nucleation centres. A further chemical requirement is a high alkaline environmental pH similar to 9-10. It is also proposed that the characteristic concentric spherical shell-like structure of spherulites, centred on primary nuclei, are due to sequential deposition of intrinsic salts, which precipitate out when the corresponding solubility limits in the liquid are successively exceeded. It can be that the better-known sedimentation of microspherulites under gravity only plays part in the final stabilization period of overall growth. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.