Energy efficient water desalination processes employing low-cost and earth-abundant materials is a critical step to sustainably manage future human needs for clean water resources. Here we demonstrate that porous silicon - a material harnessing earth abundance, cost, and environmental/biological compatibility is a candidate material for water desalination. With appropriate surface passivation of the porous silicon material to prevent surface corrosion in aqueous environments, we show that porous silicon templates can enable salt removal in capacitive deionization (CDI) ranging from 0.36% by mass at the onset from fresh to brackish water (10 mM, or 0.06% salinity) to 0.52% in ocean water salt concentrations (500 mM, or ∼0.3% salinity). This is on par with reports of most carbon nanomaterial based CDI systems based on particulate electrodes and covers the full salinity range required of a CDI system with a total ocean-to-fresh water required energy input of ∼1.45 Wh/L. The use of porous silicon for CDI enables new routes to directly couple water desalination technology with microfluidic systems and photovoltaics that natively use silicon materials, while mitigating adverse effects of water contamination occurring from nanoparticulate-based CDI electrodes.