This paper contributes to the limited existing empirical evidence on assessing household participation in Payments for Ecosystem Services (PES) programmes in developing countries. We examine this issue for the case of the Sloping Land Conversion Programme (SLCP) in China, one of the largest PES schemes in the world, using household and village level data. Our analysis examines the determinants of both current and future participation in the SLCP and makes three key contributions. First, we show the importance of incorporating the influence of programme administrators in the observed participation outcome. Secondly, we use a novel latent class approach to account for heterogeneity in the determinants of the household decision over whether to sign up to a PES programme. Thirdly, the empirical analysis focuses on the impact of market imperfections that are prevalent in developing countries. We find significant differences between households with good access to markets and those facing market imperfections.