Afforestation represents an effective approach for ecosystem restoration and carbon (C) sequestration. Nonetheless, it poses notable challenges concerning water depletion and soil drought in (semi)arid regions. The underlying mechanisms regulating the influence of afforestation on soil carbon‐water dynamics, particularly how deep soil C reacts to afforestation‐induced soil drying, remain largely unclear. This study examined the variations of soil water content (SWC), soil organic carbon (SOC), and soil inorganic carbon (SIC) in 500 cm depth along four afforestation stages: abandoned grasslands, shrublands, and 20‐year and 40‐year Robinia pseudoacacia forests (RP20 and RP40) in the semiarid Loess Plateau, China. The results indicated that afforestation has significantly increased SWC (+26.6%), SOC (+44.5%), and SIC (+6.5%) in the shallow layer (0–100 cm) but caused evident soil drying (−60.8%), decrease in SOC (−37.8%), and slight reduction in SIC (−0.3%) in the deep layer (300–500 cm) when compared with grasslands. The seriously decline in the coupling coordination between soil C and SWC in the middle and deep layers indicates the unsustainability of afforestation especially for RP40. Structural equation model showed that the negative impact of afforestation on deep SOC through soil water depletion (−0.38) outweighed the direct positive impact of increased aboveground biomass (AGB) (+0.33). The negative impacts of decreased SWC and increased pH on deep SIC was close to the positive impacts of AGB. Afforestation has different effects on SOC and SIC across shallow and deep layers, and its negative effects on deep soil C should be fully integrated into future forest ecosystem restoration and management efforts.