In this study, the allelochemical-induced effects of the leaf water extract of hemp (Cannabis sativa) on seed germination and seedling growth were investigated in durum wheat (Triticum durum) cv. Mongibello and barley (Hordeum vulgare) cv. Alamo. The seeds were imbibed in 25%, 50%, 75%, or 100% solution concentrations, obtained from a 2% hemp leaf extract, and they were germinated at 20 and 10 °C. The 2% extract stock solution (i.e., 100% solution concentration) was obtained by extracting 20 g of leaf powder in 1 L distilled water (2%, w/v). A control of seeds imbibed in distilled water was considered. Germination was scored daily and at the end of the germination test, the final germination percentage (FGP), mean germination time (MGT), germination index (GI), and vigor index (VI) were calculated. The radicles and shoots of the germinated seeds of both species were also measured for their length and weight. The analyses revealed the presence of phenols in the hemp leaf extract, which were the highest in the 100% concentration (13.14 ± 0.20 mg gallic acid equivalent-GAE g−1 extract). At 20 °C, increasing the concentration had either minor (in wheat) or no effects (in barley) on the seed germination. At 10 °C, the germination was reduced by the increasing concentration, suggesting a potential allelopathic effect of the extract. However, at 100% concentration, the seeds germinated significantly better that those at 75% concentration. At 20 °C, increasing concentration progressively depressed both the radicle and shoot elongation in both species. At 10 °C, the radicle elongation was depressed by the extract, irrespective of the concentration, whilst the shoots were as long as those of the control in wheat, and smaller at the 50 and 75% concentrations in barley. We can conclude that the water extract of hemp leaves can have a negative impact on wheat and barley seed germination and seedling growth, particularly at temperatures below optimal. However, the high concentration of phenols in the extract may stimulate seed germination and seedling growth. Thus, in semi-arid areas, such as those of the Mediterranean regions, sowings of wheat and barley after hemp at an optimal (i.e., 20 °C) or nearly optimal temperature are recommended in order to minimize the combined stressing effects of the temperature and allelopathic leaf extract upon plant establishment, which may limit a successful crop establishment.