In environments that are hostile to Global Navigation Satellites Systems (GNSS), the precision achieved by a mobile light detection and ranging (LiDAR) system (MLS) can deteriorate into the sub-meter or even the meter range due to errors in the positioning and orientation system (POS). This paper proposes a novel least squares collocation (LSC)-based method to improve the accuracy of the MLS in these hostile environments. Through a thorough consideration of the characteristics of POS errors, the proposed LSC-based method effectively corrects these errors using LiDAR control points, thereby improving the accuracy of the MLS. This method is also applied to the calibration of misalignment between the laser scanner and the POS. Several datasets from different scenarios have been adopted in order to evaluate the effectiveness of the proposed method. The results from experiments indicate that this method would represent a significant improvement in terms of the accuracy of the MLS in environments that are essentially hostile to GNSS and is also effective regarding the calibration of misalignment.