The key to restoring arid and semi-arid ecosystems is maintaining soil water and organic carbon contents. Alfalfa (Medicago sativa L.) is a high-yield perennial forage crop and performs ecological functions as a drought-resistance leguminous herb. It has been widely planted for reconstruction of degraded soils in the Loess Plateau in northwestern China, but long-term planting may affect soil carbon–water coupling and lead to crop yield reduction. To maximize the benefits of reconstructed grassland, this study explored the couplings of soil water, organic carbon, and alfalfa productivity along a reconstruction chronosequence in a semi-arid area of the Loess Plateau. Space-for-time substitution approach was used to select different-aged stands of reconstructed grassland (1, 5, 7, 10, 15, 20, 30 years old). Alfalfa above-ground biomass (AGB), soil water storage (SWS), organic carbon storage (SOCS), and carbon–water coupling coordination degree (D) were measured in the 0–100 cm soil profile. Alfalfa AGB reached a peak in the 7th year, and the degradation began in the 10th year. Both SWS and SOCS varied nonlinearly with stand age. The greatest loss of SWS occurred in the 15th year (80–100 cm depth), whereas the largest increase of SOCS occurred in the 30th year (0–20 cm depth). There was a negative feedback relationship between AGB and SWS over the 30-year study period (Pearson r = −0.835, P = 0.098). AGB and SOCS initially showed a trade-off within the first 10 years (Pearson r = −0.7431, P = 0.2569), in contrast to their positive feedback in the 20–30th years (Pearson r = 0.9978, P = 0.0421). A decoupling between SWS and SOCS (D < 0.6) was observed after 12 years of alfalfa planting. For agricultural production, a greater supply of water and organic fertilizer is required from the 7th year of alfalfa planting, and reseeding may be needed around the 10th year to prolong the life of alfalfa community. Alfalfa should be planted for no more than 12 consecutive years in the study area for ecological protection.