This paper conducts empirical study on the technical and vocational students' selecting schools based on the structural relationships of brand images, perceived values and loyalty. With questionnaire survey, freshmen from technical and vocational schools are taken as samples. The empirical study results of structural equation model show that brand image can truly exert influences on loyalty through the mediating effects of perceived values, and the mediating effects falls into full mediation effects. It indicates that brand images have direct effects on perceived values and also have indirect effects on loyalty. Therefore, stressing the effects of perceived values may produce greater effects on loyalty, which then may affect the students’ intention of selecting schools.