We report a study on the structure directing effects of functional groups and counterions. The aim was to find a facile and high yielding synthetic procedure to obtain polyoxometalate (POM) building blocks for post-functionalisation. Therefore, solvothermal reactions of VOSO₄ with various tris(hydroxymethyl)methane derivatives in alkaline methanolic solutions were investigated. In doing so, new POM fragments were isolated and characterised. The binding modes of the functionalised tripodal alkoxides turned out to be surprisingly different.