Background/Objectives: Marginal fit is a key determinant of the clinical performance of CAD/CAM (Computer-Aided DesignComputer-Aided Manufacturing) inlay restorations. This in vitro study compared the vertical marginal gap (VMG) of three chairside CAD/CAM inlay materials—VITA Enamic, CEREC Tessera, and Celtra Duo—using scanning electron microscopy (SEM) under a standardized digital workflow. Methods: Standardized Class I inlay preparations were performed in 15 extracted human molars (n = 5/material). Restorations were fabricated using a chairside workflow (Primescan intraoral scanning, CEREC 5.3 design, Primemill milling) followed by material-specific surface treatment and cementation with a self-adhesive resin cement. VMG was measured on SEM micrographs (500× for quantitative measurements; 200× for orientation) at three sites (mesial, central, distal), with three points per site (nine points/tooth; 135 point measurements). Triplicate points were averaged to site-level means and analyzed using a linear mixed-effects model (fixed effects: material, site, material × site; random intercept: tooth), Type II ANOVA, and Tukey-adjusted pairwise comparisons. Results: Mean VMG values were lowest for Celtra Duo (8.09 ± 1.98 µm), followed by VITA Enamic (27.90 ± 29.76 µm) and CEREC Tessera (32.72 ± 21.80 µm). The model indicated an overall effect of material (F(2,36) = 3.51, p = 0.040), whereas site and material × site effects were not significant. Tukey-adjusted pairwise comparisons did not reach statistical significance. Conclusions: Within the standardized chairside workflow evaluated, an overall material effect on VMG was detected, but pairwise separation was inconclusive in this sample with overlapping distributions. Celtra Duo showed smaller VMG values with narrower dispersion in overall per-tooth means, while VITA Enamic and CEREC Tessera showed wider and overlapping distributions; all group means were below commonly cited clinical acceptability ranges for marginal gap.