Inferior alveolar nerve block (IANB) is one of the most common procedures in operative dentistry, and a deep understanding of the normal anatomical variation of the pterygomandibular space (PM) is essential for its safe and successful administration. This cadaveric anatomical study aimed to use A-silicone injections to evaluate the volume of the PM. This study was conducted using 46 human cadaver heads (25 males and 21 females). A craniometric analysis was performed using the cadavers’ ages, the number of silicone cartridges (carpules) used to fill the pterygomandibular space, Izard’s Facial Index (FI), and the Cranial Index (CI). A Halstead mandibular block was performed by injecting 1.7 mL A-silicone cartridges (as an equivalent to standard local aesthetic carpules volume) into the PM. The cured silicone was extracted from the dissected mandibles. The volume (length, width, and thickness) of the extracted silicone and the number of silicone cartridges used to fill the space were evaluated. The results showed that there are statistically significant positive correlations between the CI and the width of the right PM, as well as the width and length of the left PM. A statistically significant correlation was found between the width of the left PM and the age of the cadaveric heads; the higher the age, the thicker the space on both sides. The volume of the PM corresponded to 1.5 cartridges on average.