Shrub vegetation is a key element of Mediterranean forest areas and it is necessary to develop tools that allow a precise knowledge of this vegetation. This study aims to predict shrub volume and analyze the factors affecting the accuracy of these estimations in small stands using airborne discrete-return LiDAR data. The study was performed over 83 circular stands with 0.5 m radius located in Chiva (Spain) mainly occupied by Quercus coccifera. The vegetation inside each area was clear cut, and the height and the diameter of each plant was measured to compute the volume of shrub vegetation per stand. Volume values were related with maximum height values derived from LiDAR data reaching a coefficient of determination value R2 = 0.26. Afterwards, factors affecting the quality of volume estimations were analyzed, i.e., vegetation type, LiDAR density, and accuracy of the digital terrain model (DTM). Significant accuracy improvements (R2 = 0.71) were detected for stands with 0.5 m, LiDAR data density greater than 8 points/m2, vegetation Q. coccifera, and error associated to the DTM less than 0.20 m. These results show the feasibility of using LiDAR data to predict shrub volume under certain conditions, which can contribute to improved forest management and characterization.