Transferring the intraoral situation accurately to the dental laboratory is crucial for fabricating precise restorations. This study aimed to compare the dimensional accuracy of a new hydrophilic quadrofunctional vinyl polysiloxane (VPS) and polyether (PE), in combination with different impression techniques (mono-phase single step or dual-phase single step). The reference model simulated a partially edentulous mandible. Stainless-steel precision balls were welded to specific teeth and were used to detect dimensional deviations. Fifteen impressions were made for each of the following four test groups: (1) VPS mono-phase, (2) PE mono-phase, (3) VPS dual-phase, and (4) PE dual-phase. Global accuracy was measured by deviations from the reference model, while local accuracy focused on the trueness and precision of abutment tooth surfaces. Statistical analysis was conducted using ANOVA (α = 0.05). All distances were underestimated, with the highest global inaccuracies for the cross-arch distance, ranging from −82 µm to −109 µm. The abutment tooth surfaces showed excellent local accuracy for all the materials and techniques, with crown surface trueness < 10 µm and precision < 12 µm. Inlay surfaces had higher inaccuracies (trueness < 15 µm, precision < 26 µm). Within the limitations of this study, all impression materials and techniques can be used to produce models with clinically acceptable accuracy.