The combined XAS/XRD technique has been used to investigate the stability of the microporous structure during calcination process for a series of ZnAPSO-44 materials. Incorporation of large amounts of Zn is found to produce materials that are unstable upon removal of the structure directing organic template molecule. However, simultaneous incorporation of Si is found to increase the thermal stability of the materials, yielding catalysts that are well suited for acid catalysed reactions.