Various examples of methods and systems are provided for soft sensing of system parameters in membrane distillation (MD). In one example, a system includes a MD module comprising a feed side and a permeate side separated by a membrane boundary layer; and processing circuitry configured to estimate feed solution temperatures and permeate solution temperatures of the MD module using monitored outlet temperatures of the feed side and the permeate side. In another example, a method includes monitoring outlet temperatures of a feed side and a permeate side of a MD module to determine a current feed outlet temperature and a current permeate outlet temperature; and determining a plurality of estimated temperature states of a membrane boundary layer separating the feed side and the permeate side of the MD module using the current feed outlet temperature and the current permeate outlet temperature.