(1) Background: Self-adhesive systems have been proposed for the orthodontic bonding with the intention to reduce the traditional three-component system. (2) Methods: The sample consisted of 32 extracted intact permanent premolars randomly divided into two groups (n= 16). In Group I the metal brackets were bonded with Transbond XT Primer and Transbond XT Paste. In Group II the metal brackets were bonded with GC Ortho connect. The resin was polymerized for 20 s from two directions (mesial and occlusal) using a Bluephase light-curing unit. The shear bond strength (SBS) was measured using a universal testing machine. Immediately after SBS testing, Raman microspectrometry was performed for each sample to calculate the degree of conversion (DC). (3) Results: There was no statistically significant difference in the SBS between the two groups. A significantly higher DC (p< 0.001) value was recorded in Group II, in which the brackets were bonded with GC. Very weak or no correlation (0.01) was recorded between SBS and DC in Group I and moderate positive correlation was recorded in Group II (0.33). (4) Conclusions: No difference was found in SBS between the conventional and two-step systems used in orthodontics. The two-step system demonstrated higher DC compared to the conventional system. There is a very weak or moderate correlation between DC and SBS.