The cervical area of teeth is the most unpredictable region for durable adhesive bonding. This study evaluated the adhesion potential of resin cement to coronal and cervical/root structures with a focus on enamel, dentin and cementum using etch-and-rinse and self-etch adhesive systems. Anterior teeth (N = 60) were randomly divided into six groups for adhesion tests: (a) unprepared enamel (UE), (b) ground enamel (GE), (c) mid-coronal dentin (D), (d) cervical enamel 2 mm above cementoenamel junction (CE), (e) cementoenamel junction (CEJ), and (f) root cementum (RC). Enamel and dentin surfaces were conditioned using either an etch-and-rinse (Syntac Classic-SY) or self-etch (Clearfil S3 Bond Plus-CS3) adhesive system. Resin cement (Variolink Esthetic) was adhered to the different substrates using polyethylene molds and photo-polymerized. Bonded specimens were stored in water for 24 h at 37 °C. Microshear tests (µSBT) were conducted in a Universal Testing Machine (1 mm/min) and failure types were analyzed after debonding. Data were analyzed using two-way ANOVA and t-test (alpha = 0.05). While substrate type (p < 0.001) and adhesive system (p < 0.001) significantly affected the bond results, interaction terms were not significant (p = 0.063). Within SY adhesive system, adhesion to all substrates were not significant ranging between (8.07 ± 2.39–6.80 ± 4.60) (p > 0.05), except for CEJ (5.19 ± 1.39) and RC (4.08 ± 1.13). With the CS3 adhesive system, all groups presented non-significant results (4.15 ± 1.35–6.04 + 2.38) (p > 0.05), except for D (3.57 ± 1.84) and RC (3.21 ± 1.13) (p < 0.05). µSBT values for D (7.19 ± 2.31) and RC (4.08 ± 1.13) were significantly higher for SY compared to that of CS3 (3.57 ± 1.84–3.21 ± 1.13, respectively) (p < 0.05).