In the present work we have studied the structure and the acidic properties of HZSM-5 zeolite modified with trimethyl phosphite. The modifications were carried out by using a chemical vapour deposition method as well as impregnation from n-octane solution. Both modification techniques resulted in materials with similar acidic properties. Trimethyl phosphite reacted with both Brönsted acid sites and terminal SiOH groups. The modifications resulted in the total elimination of strong Brönsted acid sites accompanied by the formation of new Brönsted type sites with decreased acid strength. However, the total acidity of the modified zeolites stayed relatively high. A possible structural transformation resulting from the phosphite modifications was proposed to be an insertion of phosphorus species between the structural aluminium- and silicon-oxygen tetrahedra. However, on the basis of 31P MAS NMR studies no evidence of the isomorphous substitution of structural T-atoms by phosphorus was found.