Oxazine-6-one and 4-pyrimidinol are two important frameworks in pharmaceutical production. Herein, we disclosed a simple, efficient, inexpensive organic base-promoted and additive-stimulated protocol for the syntheses of variably functionalized oxazine-6-ones and 4-pyrimidinols employing acetonitrile solvent under conventional heating conditions using an oil bath through C-N and C-O coupled domino steps. This simple practicable productive protocol utilizes easily producible cheap precursors, namely, benzimidates or benzamidines, with differently substituted dicyano-olefins, and it comprises step economy, robustness, and moisture insensitive conditions affording high yield that avoids the use of transition-metal catalysts, multistep with multicomponent strategy, and harsh reaction conditions involving hazardous chemicals. This method is scalable into gram-scale production with good yield.