Pharmaceutical plants contain several phytochemicals that are sources of myriad biological activities. These biological activities can be explored in multiple fields for the benefit of mankind. Pharmaceutical plants with high ethnobotanical indices (i.e., use value and relative frequency of citation) were reported with the potential to inhibit lettuce elongation through leachates and volatiles. The focus of the study was to assess Chinese pharmaceutical plants for both antioxidants, as well as allelopathic potentials to explore any underlying relationship. The estimation of antioxidative capacity and content of total phenolics (TPC) for the 55 Chinese pharmaceutical plants was conducted by the assays of DPPH radical scavenging activity (DPPH-RSA), oxygen radical absorbance capacity (ORAC) and the means of Folin–Ciocalteu. The estimation of the activity of allelopathy for collected medicinal plants was done by adopting the sandwich method for plant leachates and the dishpack method for volatile constituents, respectively. The fruits of sea buckthorn (Hippophae rhamnoides) had the most remarkable ORAC value (168 ± 7.04 μmol TE/g) and DPPH radical scavenging activity (440 ± 7.32 μmol TE/g) and contained the highest contents of total phenolic compounds (236 ± 7.62 mg GAE/g) in the 55 pharmaceutical plant species according to the results. In addition, sea buckthorn showed dominant allelopathic potential through plant leachates evaluated by using the sandwich method. Star anise (Illicium verum Hook. f.) showed conspicuous allelopathic activity through plant volatiles assessed by the dishpack bioassay method. Among the same plant species, antioxidative ability and total phenolics, in comparison with potential allelopathy of medicinal herbs indicated that volatile allelochemical had a weak active effect (r = 0.407 to 0.472, p < 0.01), with antioxidant capacity by the dishpack method. However, the evaluation by the sandwich method showed a significant positive correlation (r = 0.718 to 0.809, p < 0.001) with antioxidant capacity. Based on these results, a new hypothesis is that the antioxidant activity of plants may have an involvement with the potential allelopathic activity.