Meeting our future global energy needs in an environmentally responsible way is one of the greatest challenges in the twenty first century. The development of new materials and processes is critical to developing the needed disruptive technologies for energy conversion, delivery, storage, and use. This talk will provide an overview of recent advances from NREL on solar and electrically-driven hydrogen production from water splitting as well as carbon dioxide reduction (CO2R). Our Electrons to Molecules Initiative utilizes a large cross-section of expertise and capabilities across NREL for the purpose of utilizing electricity as an energetic driving force for the conversion of low energy molecules such as water, CO2, and N2 to generate high valued added molecules that can be utilized as either fuels, chemicals, product, and energy storage. We will also discuss R&D efforts on materials design and discovery for these and related solar energy conversion processes.