As a well-known greenhouse gas, carbon dioxide (CO₂) has attracted increasing levels of attention in areas of energy, environment, climate, etc. Notably, CO₂ is an abundant, nonflammable, and renewable C1 feedstock in view of chemistry. Therefore, the transformation of CO₂ into organic compounds is an extremely attractive research topic in modern green and sustainable chemistry. Among the numerous CO₂ utilization methods, carboxylative cycloaddition of CO₂ into propargylic alcohols is an ideal route due to the corresponding products, α-alkylidene cyclic carbonates, which are a series of highly functionalized compounds that supply numerous potential methods for the construction of various synthetically and biologically valuable agents. This cyclization reaction has been intensively studied and systematically summarized, in the past years. Therefore, attention has been gradually transferred to produce more derivative compounds. Herein, the tandem reactions of this cyclization with hydration, amination, alcoholysis, and isomerization to synthesize α-hydroxyl ketones, oxazolidinones, carbamates, unsymmetrical carbonates, tetronic acids, ethylene carbonates, etc. were systematically reviewed.