Surface engineering of crystalline silicon (c-Si) is the core of Si-based semiconductor devices. The current commercially available c-Si solar cells achieve this by making use of a conventional thin dielectric film passivation system (TDFPS), including SiO2, Al2O3, SiNx:H and hydrogenated amorphous silicon (a-Si:H) in industry. However, the TDFPS requires high-vacuum and/or high-temperature conditions, which hinders efforts to further reduce the costs of device fabrication. A revolutionized approach to circumvent these issues involves the replacement of TDFPS with new material system which can also achieve high-quality passivation on c-Si surface. Here, we successfully establish and implement a functional group passivation system (FGPS) using a series of functional materials with a sulfonic functional group -SO3H, such as 'poly(2-acrylamido-2-methylpropane-sulfonic acid)' (PAMPS) and 'polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene, sulfonated, cross-linkable' (PS-b-PERB), which can achieve a highly effective passivation on Si surface, resulting in power conversion efficiencies up to 20% when they are applied in the front surface engineering of interdigitated back contact (IBC) solar cells. Furthermore, the FGPS materials inherently allow passivation layer fabrication in low-temperature and high-vacuum-free conditions. This work provides novel low-cost material strategies without compromise of performance for c-Si surface engineering in the future Si-based photovoltaics.