Thiol-ene/acrylate shape-memory polymers can be used as base substrates for neural electrodes to treat neurological dysfunction. Neural electrodes are implanted into the body to alter or record impulse conduction. This study characterizes thiol-ene/acrylate polymers to determine which synthesis methods constitute an ideal substrate for neural implants. To achieve a desired Tg between 50 and 56.5 °C, curing conditions, polymer thickness, monomer ratios, and water uptake were all examined and controlled for. Characterization with dynamic mechanical analysis and thermal gravimetric analysis reveals that thin, thiol-ene/acrylate polymers composed of at least 50 mol % acrylate content and cured for at least 1 h at 365 nm are promising as substrates for neural electrodes.