To improve treatment efficacy of gingival recessions (GR), chemical preparation of the exposed root surface was advocated. The aim of this study was to compare the additional influence of root biomodifications with 24% ethylenediaminetetraacetic acid (EDTA) alone or with enamel matrix derivative (EMD) on the 12 month outcomes of modified coronally advanced tunnel (MCAT) with subepithelial connective tissue graft in the treatment of multiple GR. Average root coverage (ARC), complete root coverage (CRC), reduction in GR, reduction in recession width (RW), gain in clinical attachment level (CAL), increase in gingival thickness (GT), increase in keratinized tissue width (KTW) and changes in root coverage esthetic score (RES) were evaluated. A total of 60 patients with 215 GR were enrolled. In 70, GR root surfaces were treated with EDTA + EMD, in other 72, with EDTA, while in the remaining 73 saline solution was applied. ARC was 94%, 89%, and 91% in the EDTA + EMD, the EDTA and the saline groups, respectively (p = 0.8871). Gains in clinical attachment level (CAL; 2.1 ± 1.1 mm) and RES values (9.6 ± 0.9) were significantly higher in the EDTA + EMD group, when compared with two other groups. The differences between other preoperative and postoperative parameters showed statistical significance only within but not between groups. MCAT outcomes may benefit from adjunctive use of EDTA + EMD regarding 12 month CAL gain and professionally assessed esthetics using RES following treatment of GR.