An efficient ruthenium-catalyzed divergent alkylation and olefination of methyl 1,3,5-triazines with alcohols have been developed. The selectivity can be rationally tuned by the judicious choice of ruthenium catalyst, wherein Ru(PPh 3) 3 Cl 2 delivers alkylated 1,3,5-triazines and RuCl 3 gives olefinated 1,3,5-triazines in up to 98 % yield. Following this simple, facile, and high atom economical protocol, a broad range of products [a