Morphology and crystal phase evolution of GeO2 in liquid phase deposition (LPD) process is investigated. Rod-like solid phases precipitate out of solution ahead of truncated cube-like phases. SEM, XRD and TEM analyses reveal that the two sorts of solid phases are tetragonal GeO2 and hexagonal GeO2, respectively. The tetragonal GeO2 phases start to experience a re-dissolving process as soon as the hexagonal phases come into being. The prior precipitation of the rod-like phase arises from a relatively low solute saturation of tetragonal GeO2. Fast growth of a tetragonal GeO2 phase along [111] direction leads to development of a rod-like shape. The re-dissolving phenomenon does not agree with the classic growth kinetics of crystals but is strongly favored by our calculations based on thermodynamics. The GeO2 solutes are released in a fluctuant way by germanate ions, which promotes the occurrence of the re-dissolution phenomenon. The current researches open a door for room-temperature LPD growth of not only the hexagonal GeO2 particles and film but also the one-dimensional tetragonal GeO2 product. (C) 2011 Elsevier B.V. All rights reserved.