As the core of polymer chemistry, manufacture of functional polymers is one of research hotspots over the past several decades. Various polymers are developed for diverse applications due to their tunable structures and unique properties. However, traditional step‐by‐step preparation strategies inevitably involve some problems, such as separation, purification, and time‐consuming. The multicomponent reactions (MCRs) are emerging as environmentally benign synthetic strategies to construct multifunctional polymers or composites with pendant groups and designed structures because of their features, such as efficient, fast, green, and atom economy. This mini review summarizes the latest advances about fabrication of multifunctional fluorescent polymers or adsorptive polymeric composites through different MCRs, including Kabachnik–Fields reaction, Biginelli reaction, mercaptoacetic acid locking imine reaction, Debus–Radziszewski reaction, and Mannich reaction. The potential applications of these polymeric composites in biomedical and environmental remediation are also highlighted. It is expected that this mini‐review will promote the development preparation and applications of functional polymers through MCRs.