Over the course of a few decades, the concern of environmental damages of fossil fuels, an increase in CO2 emission and a decrease of hydrogen have been growing more and more. Accordingly, hydrogen production is a crucial issue nowadays. Different polymers are applied to attain the purpose. Among all polymers, biodegradables polymers are the best choices to develop the main aim. Polysaccharides and proteins are biodegradable polymers with unique places and advantages with regards to their ecofriendly properties. There are different techniques to apply and achieve the foremost purpose. It is worthwhile to mention that green and facile methods are always attracting attention in different aspects and fields. The three non-polluting and economical techniques, that is, electrochemical hydrogen evolution reaction (HER), photocatalytic technique, and hydrolysis of hydrides, are reviewed in this paper. This review helps researchers, who are environment supporters, to evaluate and choose the most ecological biopolymers and processes in their work.