Abstract: Technological and engineering literacy, as a key competency for secondary school students to adapt to future societal development, is becoming increasingly prominent. Taking Guangzhou Zhixin High School as a case study and based on the concept of cognitive apprenticeship, this study constructed and implemented a tiered and progressive curriculum system for cultivating technological and engineering literacy, exploring effective pathways to enhance high school students’ technological and engineering literacy. Pre-test and post-test questionnaires were used to assess the technological and engineering literacy and scientific literacy of 139 first-year high school students. The results showed that after the curriculum implementation, students’ technological and engineering literacy, higher-order scientific thinking, views of the nature of science, and views of scientific inquiry were all significantly improved, validating the effectiveness of the curriculum system. Accordingly, this study proposes optimization paths such as systematic construction of the curriculum system, virtual-real integration of the teaching environment, diversified innovation of teaching models, and collaborative education involving multiple stakeholders, providing theoretical support and practical reference for cultivating high school students’ technological and engineering literacy.