Biochar application emerges as a valuable soil management strategy for enhancing crop yield; however, the mechanisms underlying the relationships between soil and plants remain unclear after biochar application. In this study, soil pore characteristics and maize yield were assessed in a five-year biochar-application experiment on the Loess Plateau of China, including four treatments: Control (no biochar), low-dose biochar application (LB, 3 t ha−1), moderate-dose biochar application (MB, 6 t ha−1), and high-dose biochar application (HB, 9 t ha−1). Root growth traits were evaluated by cultivating maize in intact soil cores collected from field conditions using X-ray computed tomography. Our findings indicate that, compared to the Control, the HB treatment enhanced macroporosity (> 0.1 mm in diameter), porosity of 0.1–0.5 mm pores, and saturated water content, while reducing macropore connectivity and penetration resistance. However, biochar application treatments did not alter the water retention characteristics from field capacity to permanent wilting point or the plant-available water content (PAWC). Furthermore, the mean angle of primary and seminal roots as well as the length and surface area of entire roots increased in the HB treatment, showing a positive correlation with the porosity of 0.1–0.5 mm pores. The mean diameter of primary and seminal roots, leaf fresh and dry weights, and maize yield also increased in the HB treatment compared to the Control. Partial least squares path modeling analysis indicated that biochar application rates positively impacted on root growth and plant productivity through an indirect influence of soil pore size distribution, with 0.1–0.5 mm pores being particularly crucial for facilitating deeper root penetration and root elongation. These findings demonstrate that biochar application primarily augmented 0.1–0.5 mm pores, rather than affecting smaller pores capable of retaining plant-available water or larger macropores, enhancing deeper rooting and root elongation, thus improving plant productivity and crop yield.