Effects of electronic charge disproportionation were observed by Fe-57 Mossbauer spectroscopy at low temperatures in substituted LaFeO3 perovskites as (La1-xCax)FeO3 and La(Fe1-xMgx)O-3 (xless than or equal to0.5). The presence of both Fe3+ and Fe5+ species was evidenced in both series of compounds. Direct evidence for disproportionation was supported by correlating the Mossbauer results with the chemical determination of tetravalent iron at RT. The evolution of hyperfine parameters vs. substitution degree was comparatively analysed for Fe3+ and Fe5+ ions in relation to their electronic microscopic origin. Electron delocalisation processes are discussed in terms of ion distribution and valence state. (C) 2004 Elsevier B.V. All rights reserved.