Understanding of the structure-function relationships of natural protein channels remains a challenging task because of their unattainable physiological functions in terms of selectivity. To achieve this, a synthetic system of chemically modified channels has been constructed based on helical polymer scaffolds. Here, we report a type of positively charged channels in which multiple quaternary ammonium groups are covalently modified on the lumen surface of helical polymer while the helical conformation is intact. Compared to unmodified channels, the existence of multiple charged groups in the cavity not only makes the lumen size narrower but also essentially changes the channel properties without obstructing channel structure. Our study indicates that positively charged channels preferentially transport anions with size-dependent selectivity, whereas alkali metal ions are almost completely suppressed by electrostatic repulsion. As a consequence, a specific artificial channel with high Cl-/Na+ selectivity ratio of 41:1 is obtained.