The [AlO4/M+]0 (where M = H, Li, Na and K) defects in α-quartz have been investigated by ab initio calculations at the density functional theory (DFT) level, using the CRYSTAL06 code, 72-atom supercells, and all-electron basis sets. Our DFT calculations yielded substantially improved results than previous cluster calculations with minimal basis sets. For example, the [AlO4/M+(a<)]0 defects with M = H, Li and Na have been shown to be more stable than their [AlO4/M+(a>)]0 structural analogues (where a> and a< denote the location of the charge-compensating ion on the long-bond and short-bond side respectively), correctly predicting the common occurrence of paramagnetic [AlO4/M+(a>)]+ centres. In addition, the [AlO4/K+]0 4 defects have been investigated for the first time and are shown to be stable in quartz. Moreover, our calculations confirm previous suggestions that incorporation of the [AlO4/M+]0 defects results in significant structural relaxations that extend at least to the nearest Si atoms and give Li-O and Na-O bond distances in better agreement with the experimentally obtained values. The present theoretical results on the [AlO4/M+]0 defects provide a more complete picture for the coupled Al3+-M+ substitutions and hence new insights into crystal-chemical controls on the uptake of Al in quartz.