By virtue of the characters of rapid analysis and simple pretreatment, near infrared reflectance spectroscopy technique is widely used in agriculture, medicine, environment, petrochemical and other fields. To satisfy the rapid on-site identification and analysis, portable near-infrared spectrometers have gained more and more attention. Because near infrared reflectance spectroscopy technique also is a green tool for multi-component analysis, the paper aims at investigating the feasibility for simultaneous quantitative analysis of various heavy metal ions in dilute solution using portable near infrared spectrometer. First, amino modified polymerized starch was used as adsorbent to enrich nickel ions and copper ions in diluted solution. Then, the diffuse reflectance spectra of amino modified polymerized starch samples were measured directly by portable near-infrared spectrometer. Furthermore, with the help of spectral preprocessing methods and partial least-squares regression, quantitative models were built from the near infrared diffuse reflectance spectra of amino modified polymerized starch enriched with heavy metal ions and reference concentrations. At last, the stability of the models was proved through cross validation and external validation. The results show that nickel ions and copper ions in diluted solution can be efficiently enriched by amino modified polymerized starch in the presence of other interfering ions. The adsorption rates for nickel ions and copper ions are 99.5% and 99.8%, respectively. Two robust models can be achieved after spectra processing and partial least squares regression. The spectra processing methods contains Continuous wavelet transform and multiplicative scatter correction combined with Savitzky-Golay. The obtained corresponding correlation coefficients of the two robust models are 0.981 9 and 0.965 4, respectively. Thus, simultaneous quantitative analysis of nickel ions and copper ions in the mixed diluted solution was achieved, and the detectable concentrations of nickel ions and copper ions are both as low as 3.0 mg·L-1. The method not only improves the sensitivity of near infrared reflectance spectroscopy technique, but also demonstrates the feasibility for simultaneous quantitative determination of various heavy metal ions by using portable near infrared spectrometer. Moreover, the method may be a useful exploration to further broaden the application of near infrared reflectance spectroscopy technique.