As the world’s population increases, the demand for energy also grows. The strain on our limited resources of fossil fuels is unsustainable in the long term. An alternative, renewable method of energy generation must be implemented. Solar energy has good potential as an environmentally sound, unlimited energy source, but solar devices are not yet able to efficiently store energy for later use. A device has been proposed which uses direct sunlight to split water into hydrogen and oxygen. The hydrogen can then be harvested and stored as fuel, solving the question of how to effectively store energy generated during times of peak sunlight for use when sunlight levels are low. The prototype device incorporates arrays of doped silicon microwires which function as light absorbers and current-carriers, driving the chemical reactions that evolve hydrogen from water. This work aims to quantify and characterize the reduction in microwire resistivity that is achievable through application of silicon’s piezoresistive properties. Silicon displays a change in electrical resistance as a function of applied mechanical strain. This electromechanical effect has been studied extensively in bulk and top-down (etched) microstructures, but studies on microstructures grown bottom-up have been limited. A simple method is presented for piezoresistive characterization of individual, released, bottom-up silicon microwires. It is shown that these n-type microwires display a consistent negative piezoresistive response which increases in magnitude with increasing doping concentration. It was found that harnessing the piezoresistive response of moderately-doped (∼10^17 cm^−3) n-type wires allowed for a maximum observed reduction in resistivity of 49%, which translated to a 1% reduction in overall system resistance of a prototype unit cell of the artificial photosynthesis device, if all other components therein remained unchanged.