Formaldehyde aqueous solution can act as an effective photoinitiating system for water-borne photo-grafting. The photografting of acrylic acid (AA) and methacrylic acid (MAA) onto high-density polyethylene (HDPE), low-density polyethylene (LDPE) and polypropylene (PP) initiated by formaldehyde aqueous solutions has been reported. The effects of formaldehyde content and monomer concentration on grafting varied with the polymeric substrates and monomers used. For the grafting of AA onto HDPE, the extent of grafting increased with increasing formaldehyde content in the solution, monomer concentration had a little effect on grafting. Whereas for the grafting of MAA onto HDPE, the grafting performed in 8% formaldehyde aqueous solution lead to the highest extent of grafting, the extent of grafting increased with monomer concentration till 2.5 mol/L. MAA was easier to be grafted onto the polyolefins than AA. The easiness of grafting occurring on the polyolefins was in a decreasing order of LDPE > HDPE > PP. Qualitative and semi-quantitative Fourier transform infrared (FTIR) characterizations of the grafted samples were performed. For both grafted LDPE and PP samples, at the same irradiation time, the carbonyl index of the samples grafted with MAA was higher than that grafted with AA. The FTIR results are in accord with the results obtained by gravimetric method. The water absorbency of the grafted samples increased almost linearly with the extent of grafting. The PE films grafted with AA adsorbed more water than those grafted with MAA. This study had broadened the water-home initiating system for photografting. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 113: 2062-2071, 2009