Effects of aging after pyrolysis were tested relative to the physicochemical characteristics of peanut straw biochar. Biochar was prepared at pyrolysis temperatures of 350 °C, 500 °C, and 650 °C; then, it was freeze-thawed and dry-wet aged. The physicochemical characteristics of the fresh and aged biochar were analyzed. The results showed that the pyrolysis temperature, ambient temperature, and humidity affected the physicochemical characteristics of the biochar. With the increase of pyrolysis temperature, the yield and surface acidic functional groups of the fresh biochar decreased, whereas the ash content, C content, pH, specific surface area, and mesoporous volume of the fresh biochar increased. The aging treatment increased the acidic functional groups content in the biochar and reduced the aromatic functional groups content, which decreased the pH value of the biochar. The aging treatment increased the specific surface area and pore volume of the biochar, and the effect of freeze-thaw aging was greater than that of dry-wet aging. The aging treatment also destroyed the complete shape of the fresh biochar, and reduced its stability. After the aging treatment, the C content of the biochar decreased, whereas the O content increased, due to oxidation of the biochar.