Tertiary amines represent a key class of organic molecules with multiple industrial, synthetic, and analytical applications. The focus of this review is on different approaches towards the synthesis of the C 3 and C 3V symmetrical tertiary amines. Generally, symmetrical tertiary amines can be prepared via N‐alkylation with alkyl halides and alcohols, reductive amination, desamination, hydroamination of olefins, and different kinds of C–N cross‐coupling reactions. All reactions leading to the titled structures are discussed, and the advantages and disadvantages of each method are provided.