The quality of dental arch impression has a substantial role in the precision of the intervention. It is traditionally acquired with resins that solidify when in contact with the air. Compared to that method, digital impression gives great advantages and, together with three-dimensional (3D) digitization devices, allows a simplification of the digital impression process. The growing adoption of such systems by a large number of dental clinics determines the need for an in-depth evaluation of the accuracy and the precision of the different systems. The aim of this work is to define a methodology for the evaluation of the accuracy and precision of 3D intraoral and desktop scanning systems, by using volumetric and linear methods. The replica of a tooth was realized with zirconium; afterward, high-accuracy point clouds of the master model were acquired by a coordinate measurement machine (CMM). In this way, the dimensions of the replica were accurately known. An intraoral scanner (I) and three desktops (D1, D2, D3) were then used to scan the replica. The geometry resulting from the CMM was compared with the ones derived from the scanners, using two different commercial programs (Geomagic and 3-Matic) and a custom-developed algorithm (MATLAB). Geomagic showed the mean values to be in a range from 0.0286 mm (D1) to 0.1654 mm (I), while 3-Matic showed mean values from −0.0396 mm (D1) to 0.1303 mm (I). MATLAB results ranged from 0.00014 mm (D1) to 0.00049 mm (D2). The probability distributions of the volumetric error of the measurements obtained with the different scanners allow a direct comparison of their performances. For the results given by our study, the volumetric approach that we adopted appears to be an excellent system of analysis.