Plant lignification is a tightly regulated complex cellular process that occurs via three sequential steps: the synthesis of monolignols within the cytosol; the transport of monomeric precursors across plasma membrane; and the oxidative polymerization of monolignols to form lignin macromolecules within the cell wall. Although we have a reasonable understanding of monolignol biosynthesis, many aspects of lignin assembly remain elusive. These include the precursors' transport and oxidation, and the initiation of lignin polymerization. This review describes our current knowledge of the molecular mechanisms underlying monolignol transport and oxidation, discusses the intriguing yet least-understood aspects of lignin assembly, and highlights the technologies potentially aiding in clarifying the enigma of plant lignification.