The aggregation of hydrogen fluoride vapor is explored through the use of Monte Carlo simulations employing Kohn-Sham density functional theory with the exchange/correlation functional of Becke-Lee-Yang-Parr to describe the molecular interactions. Canonical ensemble simulations sampling the classical phase space were carried out for a system consisting of ten molecules at constant density (2700 Å3/molecule) and at three different temperatures (T = 310, 350, and 390 K). Aggregation-volume-bias and configurational-bias Monte Carlo approaches (along with pre-sampling with an approximate potential) were employed to increase the sampling efficiency of cluster formation and destruction. A hydrogen-bond analysis shows that about two thirds of the HF molecules are part of small aggregates at 310 K, whereas only about 10% of the molecules are clustered at 390 K. As for other hydrogen-bonding systems, the size distribution exhibits some sensitivity to the criteria used to define a hydrogen bond, but the qualitative features are not affected by these differences. From the temperature dependence of the equilibrium constants, the dimer and trimer aggregation energies (not corrected for nuclear quantum effects) are estimated using a simple distance-based hydrogen-bonding criterion as -13 ± 3 and -65 ± 16 kJ mol-1, respectively, whereas these binding energies are found to be somewhat different for a combined distance-angular criterion with values of -17 ± 6 and -63 ± 11 kJ mol-1, respectively. The strictness of the hydrogen-bonding criterion plays a significant role for the assignment of clusters to linear, cyclic, and branched architectures with the fraction of the latter being drastically reduced for the distance-angular criterion. The average molecular dipole moment increases from 1.85 Debye for isolated molecules to about 2.0 D for dimers to about 2.75 D for larger aggregates, and the H-F bond length shows a concomitant, but smaller increase from about 0.94 to 0.98 Å.