In this study, a multimedia web-based English learning (MWBEL) system is implemented to assist undergraduate English learning as second language acquisition (SLA). The objectives of this study are to help the MWBEL system developers and university staffs to recognize what factors actually influence college student’s intentions to use such a virtual learning environment. The research results indicate that students in SLA courses hold positive motivations towards the MWBEL system and exposed a possible benefit from its use in the long run. However, they also convey some negative opinions of the MWBEL system, suggesting additional improvement of the relative underlying factors of multimedia web-based English learning.