In primary science education, inquiry‐based science instruction stands out as an optimal learning environment for fostering domain‐specific content and procedural knowledge. Recognizing the effectiveness of different forms of teacher guidance, there is an ongoing debate about the planning of high (structured inquiry) and low (guided inquiry) guidance and their optimal sequencing. This debate revolves around balancing the level of autonomy and the amount of conceptual information given to students. Furthermore, the complete understanding of the impact of responsive teaching, which encompasses a broad range of practices, including on‐the‐fly scaffolding such as Promoting Participation, Focusing, and Problematizing, remains elusive. To address this gap, this study examines the relationship between planned teacher guidance and specific instances of responsive teaching, particularly on‐the‐fly scaffolding in the inquiry‐based science classroom. A pre‐posttest design was employed, involving 164 primary school students (M = 9.9 years, SD = 0.66, 57% female) and one female experimenter. Domain‐specific content knowledge contained science concepts of thermal insulation, whereas procedural knowledge comprised the application of the control‐of‐variables strategy. The sequential order of planned teacher guidance, structured inquiry, and guided inquiry, was systematically varied, and the experimenter was allowed to provide spontaneous on‐the‐fly scaffolding. The study assesses the influence of planned teacher guidance and specific instances of responsive teaching, particularly on‐the‐fly scaffolding on students' conceptual and procedural knowledge. Results indicate no differential learning effects based on the order of planned guidance. However, when planned guided inquiry was provided second, the teacher gave less on‐the‐fly scaffolding. Additionally, Problematizing had a positive effect, while Focusing had a negative effect on students' procedural knowledge learning.