<p>The development of efficient alkyne-based polymerization techniques is of great significance due to their broad applications in synthetic chemistry, biomedicine, and materials science. Among these, the polymerization of dual-activated alkynes has emerged as a powerful strategy for synthesizing multifunctional polymers with tailored properties. This review systematically summarizes recent advances in polymerization methodologies involving dual-activated alkynes, including mechanistic insights, optimization strategies, and structural diversification approaches. Representative examples are provided to illustrate the design principles and reaction pathways of each polymerization approach. Furthermore, the unique physicochemical properties of the resulting polymers, such as aggregation-induced emission (AIE), high refractive index, and stimuli-responsiveness, as well as their applications in optoelectronics, bioimaging, drug delivery, and energy storage, were highlighted. By establishing clear correlations between synthetic approaches and functional outcomes, this review aims to inspire the rational design of novel polymeric materials.</p>