Green roofs contribute to more sustainable cities, but current commercial substrates suffer from important limitations. If carefully selected, biochar could serve as a viable option for a more sustainable green roof substrate. We propose a protocol to select an optimal biochar for green roof substrate amendment. Coffee husks, medium-density fiberboard, palm date fronds, and a mixture of waste wood, tree bark, and olive stone kernels are selected as residues for biochar production to develop a selection protocol. The residues are pyrolyzed at 350, 450, 500, and 550 °C in a lab-scale reactor. A pyrolysis temperature of 450 °C is selected for upscaling and is based on biochar yield, pH, salinity, and elemental composition. From evaluating the biochar characteristics after upscaling, it can be concluded that the biochar’s carbonization degree is mainly controlled by pyrolysis temperature, while yield, pH, and salinity are more dependent on the biomass properties. Ultimately, our procedure evaluates the presence of important contaminants, the biochar’s water holding capacity, salinity, pH, and carbonization degree. To validate the developed protocol, plant coverage experiments on green roofs are performed, which are quantified using a novel digital image processing method, demonstrating its efficient use to facilitate future biochar selection in substrates.