This paper uses a Probit regression model to empirically examine the characteristics of participants in upper-secondary technical and vocational education (TVE), relative to upper-secondary academic schools. Using a nationally representative dataset from China, this study finds that compared with academic schools, participants of upper-secondary TVE tend to come from relatively disadvantaged family backgrounds, particularly in terms of parental education levels. Given TVE enrols a significant proportion (38%) of students at the upper-secondary level, these findings call for government policies aimed at improved equality in education access. This study also finds that students of secondary specialised schools, the most selective type of TVE schools, are more likely to be females. This first empirical study on TVE enrolment in China, the largest developing country, significantly adds to the literature on vocational education.