In aqueous solution, the stability, the structure, and the lability of 12 vanadium(V) complexes were determined and related to the amino alcohol ligand properties. The amino alcohols were chosen to maintain a five-coordinate vanadium geometry in the vanadium complex and were based on diethanolamine as the parent ligand. Apparent and composite stability constants were determined for all 12 complexes. Selected complexes were further examined to determine solution structure, lability, and thermodynamic properties. We empirically show that the formation constants for the series of 12 complexes, when plotted as a function of the pK(a) value for the protonated amino alcohol, generate a curve that initially increases as the pK(a) value increases and then decreases as the pK(a) value continues to increase. The observed associations suggest that the electron-donating capacity of the amino alcohol plays a major role in complex stability; however, metal coordination number, sterics in the amino alcohol, and solvation also are found to affect the stability. Determination of the thermodynamic parameters of selected complexes showed that the enthalpic component was the major contributor to the stability of the complex, but that the entropic component opposed this term. A series of studies was conducted to examine whether the lability of these complexes varied from the parent complexes. Unfortunately, the variation in the lability of these complexes was much less than the variation in complex stability. In summary, these studies describe quantitatively the variation in complex stability and lability as the structure of amino alcohol is modified and explain why some complexes show less stability than predicted on the basis of the pK(a) value. In short, this study provides valuable information for the design of additional vanadium complexes with specific properties.