The gelation properties and gel structure of purified salep glucomannan (S) blended with xanthan (X) in different ratios (3:1, 1:1, and 1:3) and at various pH values (water, pH 5.5 and pH 4.0) were investigated. The results indicated that the gelation temperature was rate-independent in varied environments, but the sol-gel transition temperature determined in water and at a pH of 5.5 decreased from 58 to 53 °C when the pH was 4.0. The early structural development of highly concentrated xanthan solutions was observed during the cooling process. In the gelled samples, 3XS and XS had more linear viscoelastic regions and higher yield stress values than 3SX when more stress was applied and the pH decreased. The gel was strong at a low frequency but weak at a high frequency. The early transition frequency of these gel types was observed for 3SX at low pH values, indicating that it had fewer junction points, and the average size of the junction points in the gel network were lower. The melting temperatures of the gels showed the thermo-sensitive behavior of the gels, which was determined to be higher for 3XS due to the stronger and more abundant junction zones. Thus, 3XS had a higher thermal stability than XS and 3SX. Other data supporting this result were observed by determining the creep-recovery parameters, color and gel strength values. The synergistically interacting salep-xanthan gels were shown by FTIR and these gels exhibited high water holding capacities. The usage of the same proportion of polymers and high salep ratios seems more preferable in the water system, while higher xanthan ratios were needed at low pH values if better a gel behavior was desired, such as for the potential use of these materials in food and biomedical applications.