From the measured 127I Mössbauer spectra, we have determined the isomer shift, quadrupole coupling constant, and recoilless fraction for CH3I, CF3I, C6H5I, o‐, m‐, and p‐C6H4FI, and C6F5I. From relative intensities of the peaks, there is evidence for either orientation or Goldanskii‐Karyagin effects in CH3I, CF3I, and φI. The isomer shifts and quadrupole coupling constants give values for the numbers of p and s holes, from which the charge and hybridization of iodine in these compounds is calculated. Except for C6F5I, the charges correlate well with the pKa of corresponding carboxylic acids. It is suggested that the anomalous behavior of this compound arises from the formation of a charge transfer complex in the solid. From a comparison of NQR and Mössbauer data for CI4 and CF3I, an explanation is suggested for the anomalous decrease of chlorine NQR frequencies in the series of compounds CFn Cl4−n (n = 0→3). The problem of deriving meaningful Mössbauer parameters from complex spectra taken with thick absorbers is discussed.