To investigate the recreation of Bronsted acid sites in phosphorus-modified HZSM-5(Ga) zeolites by modification with various metal cations, we prepared several HZSM-5(Ga) zeolites co-modified with Mg, Ca, La or Zr and P (M/P/HZSM-5(Ga)). From FT-IR,P-31 MAS NMR, and NH3-TPD measurements, it was found that the introduced metal cations (M) of Mg, Ca, La, and Zr react with the pre-introduced phosphorus to generate phosphorus species such as M-x(PO4)(y), resulting in the recreation of some native Bronsted acid sites (Si(OH)Ga). The degree of recreation of the Bronsted acid sites was strongly dependent on the M/Ga ratio and doped metal valence. Modification with La and Zr that have higher valences more effectively recreated the Bronsted acid sites compared to Mg and Ca, which have di-valence. The conversion of ethanol to propylene was carried out over the M/P/HZSM-5(Ga). The propylene yield increased with increasing M/Ga ratio and reached maximum values of ca. 26 C-% for Zr/P/HZSM-5(Ga) with a Zr/Ga ratio of 0.25 and ca. 29 C-% for La/P/HZSM-5(Ga) with a La/Ga ratio of 0.4. The propylene yield hardly changed for the co-modified HZSM-5(Ga) zeolites during the 24 h of reaction time, indicating the suppression of both carbonaceous deposition and the release of gallium from the zeolite framework. (C) 2014 Elsevier B.V. All rights reserved.