Unit pricing for domestic waste, or pay-as-you-throw (PAYT), affords a promising policy option for waste classification and reduction at source. As an emerging economy, China intends to adopt the sophisticated instrument of unit pricing. The public attitude to this policy is of high relevance for its actual implementation. For the first time in China, this paper quantitatively examined the acceptability of the policy among urban residents by randomly delivering 632 questionnaires by taking Beijing, a megacity expected to introduce the practice, as an example. Based on the ordered logit model, determinants of acceptability were empirically tested including intrinsic, external and demographic factors. The results show that the acceptability rate of PAYT in Beijing is less than half, with the proportion of firm support reaching only 42.6%. The respectively low acceptability rate indicates substantial compliance costs, due to intensive resistance to policy implementation and more resources to be invested to promote acceptability. Empirical analysis further indicates that (1) regarding demographic features, aged or less educated residents tend to accept unit pricing, (2) as for intrinsic factors, a friendly environmental attitude, deeper understanding of charging policy and better social perception can significantly improve the public acceptability of the policy, and (3) in terms of external factors, better property services and transparent funding mechanisms play significant roles in enhancing public acceptability. These findings are further confirmed by replacing the dependent variable with either the willingness to pay for household waste disposal or the acceptability of the operated sewage treatment fee. The status of residents’ preference for specific pricing methods is further investigated with underlying reasons being revealed. For developing regions with an urgent demand for waste reduction, it is proposed to install unit pricing in time to avoid possible growing social acceptability costs. Specific measures are proposed including changes in intrinsic factors, paying attention to focus groups, and building social consensus for unit pricing.