Development of next generation electrochemical devices such as solid oxide cells requires control of the charge transfer processes across key interfaces. Structural strain at electrolyte:electrode interfaces could potentially alter the devices charge transport properties, therefore understanding the structural behaviour of electrode surfaces at operating conditions is important. The functional oxide single crystal substrate SrLaAlO4 has been well-characterised with bulk structure studies, however there are very few studies of SrLaAlO4 surface structures. Here we present an investigation of the surface structure of SrLaAlO4(001) substrates using surface X-ray diffraction, under UHV conditions (10−10 torr) with the substrate held at either room temperature or 650 ◦C. Best-fit models using a 1:1 ratio of Sr:La showed significant distortions to the surface AlO6 octahedra.