The new curriculum standards have put forward new requirements for high school English vocabulary teaching, and the English vocabulary eco-classroom under the guidance of ecological linguistics theory can precisely make up for the shortcomings in the traditional vocabulary classroom and meet the challenges of the times. However, most of the existing researches on ecological classroom are combined with macro English subjects, and few of them are about English vocabulary teaching. This study takes the principles of ecological linguistics as the theoretical basis to support the conceptual construction and morphological reliance of the vocabulary ecological classroom, supplemented by modal theory as the process orientation of the four major stages in the teaching process, constructs a new vocabulary ecological classroom model based on Markov chain model, and applies the ecological classroom model to high school English vocabulary teaching to verify its teaching effects. The experimental results show that the Markov chain-based high school English vocabulary teaching under the “ecological linguistics” model can help students’ interest in vocabulary learning and promote their vocabulary learning level, accounting for 15% improvement in the learning effect.