Crystalline silicon (c-Si) solar cells have dominated the photovoltaic market due to their superior mechanical and thermal robustness, nonhazardous nature, optimal energy bandgap, and the availability of established manufacturing techniques. However, conventional c-Si solar cells fabricated through thermal doping processes present challenges such as high recombination rates and increased production costs. Recently, dopant-free solar cells have emerged as a promising next-generation approach; they offer numerous advantages, such as reduced recombination, cost-effectiveness, environmental friendliness, and applicability to nano- and submicrometer structures. This review evaluates the strengths and weaknesses of dopant-free passivating contact materials for emitters, tracing the development of dopant-free solar cells from the earliest reports to the current state-of-the-art. A systematic evaluation of these materials based on their electrical and optical properties, coating conformality, stability, and overall photovoltaic performance is presented. Moreover, the limitations of dopant-free solar cells are identified and strategies to further enhance their efficiency are proposed. Dopant-free crystalline silicon solar cells exhibit multiple advantages, including reduced recombination, cost-effectiveness, environmental friendliness, and applicability to nano- and submicrometer structures. This review discusses the evolution of dopant-free solar cells, operating principles underlying their functioning, key characteristics of materials used to form junctions in the cells, and strategies for improving their efficiencies.image (c) 2023 WILEY-VCH GmbH