Concrete structures in service are often subjected to environmental/operational temperature effects, which change their inherent properties and also inflict a challenge to their extrinsic monitoring systems. Recently, piezoelectric lead zirconate titanate (PZT)-based electromechanical admittance technique has been increasingly growing into an effective tool for concrete structural health monitoring; however, uncertainty in the changes of monitoring signals induced by temperature impact on concrete/PZT sensor would inevitably cause interference to structural damage detection, which adversely hinder its application from laboratory to engineering practice. This article, aiming at exploring the temperature effect on the electromechanical admittance–based concrete damage evaluation, primarily covered a series of theoretical/numerical analysis with rigorously experimental verifications. Three aspects of comparative studies were performed in theoretical/numerical analysis: (1) thermal-dependent parameters were inclusively evaluated in contribution to the electromechanical admittance characteristics via PZT-structure interaction models; (2) three-dimensional finite element analysis in multi-physics coupled field was employed to qualitatively assess the singular temperature effect on the electromechanical admittance behaviors of free-vibrated PZT, surface-bonded PZT/inside-embedded PZT coupled healthy concrete cubes; and (3) depending on the modeling of surface-bonded PZT-/inside-embedded PZT-cracked concrete cube, thermal effect on damage evaluation was addressed via quantification on the electromechanical admittance variations. In the experimental study, rigorous validation tests were carried out on a group of lab-scale concrete cubes, where surface-bonded PZT/inside-embedded PZT transducers were simultaneously employed for electromechanical admittance monitoring in view of thermal difference between concrete surface and its inner part. Correlation coefficient deviation value-based effective frequency shifts algorithm was also employed to compensate the temperature effect. Moreover, temperature effect was further testified on the monitoring of a full-scale shield-tunnel segment structure. Experimental results indicated that temperature triggered different behaviors of electromechanical admittance signatures for surface-bonded PZT/inside-embedded PZT transducers and contaminated the electromechanical admittance responses for damage detection. Structural damage severity level can be disadvantageously amplified by temperature increment even if under the same damage scenarios.