This paper presents an innovative teaching approach that integrates photoelectric technology with analytical chemistry instruction through inquiry-based learning (IBL), using cerium as a selected analyte. With the advancement of science and technology, a strong foundation of basic knowledge and methodologies is crucial in analytical chemistry education. Spectrophotometry and coulometric titration are key instrumental analysis methods representing relative analysis and absolute analysis, respectively. Utilizing light and electricity, these methods provide platforms for deep exploration. To transcend traditional teaching methods, we adopted IBL, where students, stimulated by real-world problems, actively engage in the learning process. Cerium, chosen for its unique properties and wide applications, is an ideal subject for experimental analysis. Through experimental design, students use spectrophotometry and coulometric titration to measure the cerium content and explore various factors. This approach reinforces chemical equilibrium knowledge and enhances students' experimental skills, data analysis abilities, and scientific literacy. The 32 h course, spread over five sessions, promotes independent learning and teamwork. By applying IBL, we aim to ignite students' enthusiasm, deepen their understanding of foundational concepts, and prepare them for future analytical chemistry pursuits. This practice promises to enhance students' practical skills and scientific literacy, capturing the interest of chemistry educators and professionals.