We consider the problem of estimating the parameters of a Markov Random Field with hard-constraints using a single sample. As our main running examples, we use the $k$-SAT and the proper coloring models, as well as general $H$-coloring models; for all of these we obtain both positive and negative results. In contrast to the soft-constrained case, we show in particular that single-sample estimation is not always possible, and that the existence of an estimator is related to the existence of non-satisfiable instances. Our algorithms are based on the pseudo-likelihood estimator. We show variance bounds for this estimator using coupling techniques inspired, in the case of $k$-SAT, by Moitra's sampling algorithm (JACM, 2019); our positive results for colorings build on this new coupling approach. For $q$-colorings on graphs with maximum degree $d$, we give a linear-time estimator when $q>d+1$, whereas the problem is non-identifiable when $q\leq d+1$. For general $H$-colorings, we show that standard conditions that guarantee sampling, such as Dobrushin's condition, are insufficient for one-sample learning; on the positive side, we provide a general condition that is sufficient to guarantee linear-time learning and obtain applications for proper colorings and permissive models. For the $k$-SAT model on formulas with maximum degree $d$, we provide a linear-time estimator when $k\gtrsim 6.45\log d$, whereas the problem becomes non-identifiable when $k\lesssim \log d$.