Early years experiences in quality thinking and socialization are critical to the optimal development of children, and Quality Early Childhood Education (QECE), is crucial in achieving these quality developments. However, several literatures suggest that there is a general lack of Teaching and Learning Materials (TLMs) in Sub-Saharan Africa, Ghana inclusive. Meanwhile, the constructivists' theory and other researches indicate that to ensure QECE, TLMs should be available and accessible to learners to interact with in advance and during a lesson. Using case study design therefore, data in the form of interview and observation were collected from twelve ECE schools in the Agona East District of the Central Region of Ghana. Participants composed of twelve ECE teachers and twelve head teachers of the schools totalling twenty-four. The findings suggest that participants perceived TLMs as very important factor in ensuring QECE provision. Again, TLMs were not readily available and so the children could not interact with them. The study further revealed that the unavailable nature of the TLMs hindered children's accessibility and active interaction with them. The findings further revealed that interaction could not feature prominently in the provision of the ECE due to unavailability and inaccessibility of TLMs. Based on the findings, it is suggested that teachers and providers of ECE should ensure that TLMs are made available and accessible to learners to interact with. Teachers should also devise innovative ways of creating and developing TLMs from their locality. Moreover, they should encourage and promote children's active interaction with the TLMs, as this is a sure way of achieving learning.