In this paper we investigate values and transaction conditions in consumer participation in alternative food networks (AFNs). We use and combine a collective action perspective with elements of ethical consumption (individual values) and transaction cost economics as a theoretical background to conceptualise this participation. Our research is motivated by the evidence that the role and interplay between values and transaction conditions is still under-investigated in the socio-economic literature when it comes to understanding participation in AFNs. We use a case study in which we focus on an AFN located in Palermo, a metropolitan area in southern Italy. We collected data related to 303 individuals: 103 participants in the AFN and 200 non-participants. From a methodological perspective we used a propensity score matching approach. We were thus able to build a subsample consisting of only those individuals who were sharing a similar likelihood of participating in an AFN. Individuals with the same propensity score show a substantial equivalence in terms of covariates as if they were randomly selected to join an AFN. Our results indicate a statistically significant difference in some transactional conditions for AFN participants. Namely, when it comes to transactional conditions associated to food purchasing strategies, participants in AFNs are characterised by a higher level of (perceived) information uncertainty (e.g. price uncertainty and product information), negotiation uncertainty (e.g. relevance of the speed of sourcing, transportation hazards, and bargaining), and monitoring hazards (e.g. quality uncertainty), when compared to non-participants. These results are used to account for the heterogeneity of participants in SPGs in particular, and AFNs in general.