Exploration of efficient and powerful polymerization methodologies is of crucial importance for polymer science. Among the established polymerization methodologies, the polymerization of internal alkynes is less developed and still in its infancy stage. In this work, a new polymerization of internal alkynes of bromoalkynes and phenols is established, and polymers with high weight-average molecular weights (up to 47 600) are obtained in excellent yields (up to 95.2%) in as short as 1 h without using a complex transition-metal catalytic system. The resultant polymers possess good solubility, exhibit high thermal stability, and could display typical aggregation-induced emission (AIE) characteristics upon introduction of tetraphenylethylene, a typical AIE-active luminogen. Moreover, the polymers could be post-modified by a thiophenol derivative because they contain bromovinyl groups in each repeating unit, enabling it to possess a higher refractive index than that of the pristine one. Therefore, it displays a convenient platform for polymer functionalization. This work not only establishes a new polymerization of bromoalkynes and phenols but also provides a powerful strategy for the preparation and modification of functional polymers under mild reaction conditions without using transition-metal catalysts.