This thesis examines the impact of both substrate fabrication method and self-assembled monolayer (SAMs) identity on the stability of microcavity array supported lipid bilayer, on two separate microcavity array platforms. The presented study investigates the gold electrochemically deposited microcavity arrays and their capacity, after aqueous filling to support lipid bilayer membranes using lipid bilayer assembly methods previously reported. The impact of SAMs with varying end termini at two different types of microcavity array platforms on membrane stability was examined. Membrane stability was explored using electrochemical impedance spectroscopy (EIS) while membrane presence and formation was confirmed using Raman spectroscopy and cyclic voltammetry (CV). Chapter 1 gives a background to the thesis. The chapter introduces SAMs, describes their basic properties and the impact they can exert on a metal interface and then discusses the different types of cell membrane models currently applied. It also covers the electrochemical methods used in this thesis to assess monolayer assembly and the lipid bilayers. Limitations of the current models are described with respect to stability. vii Chapter 2 investigates the use of SAM with differing end termini on polystyrene sphere templated electrochemically deposited microcavity array supported lipid bilayer (MSLB). Fabrication methods are described for electrochemically mesopore arrays and their functionalisation with 6-mercapto-1-hexanol, hydroxyl-terminated polyethylene glycol (PEG) thiol and 6-mercaptohexanoic acid SAMs using microcontact printing (μCP). These modified arrays were investigated as whether they could support stable lipid bilayers prepared using the Langmuir-Blodgett method to form the first monolayers followed by vesical disruption to form a lipid bilayer. In Chapter 3, an alternative microcavity array platform was fabricated using a two-photon polymerisation technique and its ability to support a lipid bilayer was examined as a function of SAM support using μCP as a functionalisation method. DOPC membranes were successfully spanned across a microcavity array platform through μCP using the same SAMs used in chapter 2. Overall, this thesis demonstrates a new way to selectively modify the top surface of the gold cavity arrays using different types of substrates using 6-mercapto-1-hexanol, hydroxyl terminated PEG thiol and 6-mercaptohexanoic acid. Through EIS the stability of lipid bilayers on MSLBs using different SAMs with different end terminus on both was assessed on both sphere lithography electrochemically deposited and two-photon polymerisation fabricated microcavity arrays.