A new kind of polyacrylamide derivate, hydroximic polyacrylamide (HPAM), was prepared from polyacrylamide (PAM) with hydroxylamine hydrochloride in KOH/alcohol solution. Based on colorimetric method in the measurement of C_7–9alkyl hydroximic acid, the substitution degree of HPAM was determined by selecting octyl hydroximic acid as a primary standard substance. The effects of temperature, the amount of hydroxylamine and potassium hydroxide, and the reaction time on the reaction are discussed. HPAM with 5.78% substitution of degree was acquired by optimizing the reaction conditions. IR spectra revealed that tautomerism appears in the HPAM, and that HPAM exists in both the forms of hydroxamic type and hydroximic type, and the latter type can easily lead to the forming of intramolecular hydrogen bond.