Millimeter-sized mercury iodide crystals were obtained by the isothermal evaporation technique using dimethylformamide (DMF), diethyl-ether/DMF mixture and THF. Different concentrations (18mM and 400mM) and solution temperature (25–80°C) were used to obtain varied evaporation rates (0.1×10−4–5000×10−4ml/h). Different crystal sizes and shapes were obtained by changing solvents, mixture and initial solution volume. According to X-ray diffraction the samples are monocrystalline. The top surface was investigated by SEM. Optical band-gaps above 2eV were obtained from photoacoustic spectroscopy. Photoluminescence spectra indicated band-to-band electronic transitions, and the presence of sub-band gap states. Excitons, structural defects and the presence of impurities are discussed and correlated to the electrical measurements. Crystals obtained using pure DMF as solvent showed better general properties, including under the exposure to mammographic X-ray energy range that led to sensibility of about 25μC/Rcm2.