Mobile applications such as multimedia messaging service (MMS) promises a new way to share rich content of information that enhances its users’ personal connectivity experiences as well as productivity. However, the adoption of MMS seems to be unexpectedly slow (Bonte, 2008). As mobile phones become ever smarter (or complex) in functions, understanding the adoption behaviors of complex mobile services such as MMS becomes utterly important to both practitioners and academic. This chapter introduces a multi-facet model for MMS adoption by integrating the well-known behavioral models such as TAM and TPB with other factors including intrinsic motivation, personal innovativeness and critical mass. An internet survey of 213 subjects with prior experience in MMS usage found strong support for the proposed model. The results show that the adopter’s attitude toward MMS is the most dominating factor in shaping his/her intention to use MMS, followed by subjective norm and perceived behavioral control. Moreover, the results further suggest adopter’s intrinsic motivation is the most important motivating factor for attitude toward using MMS. Implications of these findings are discussed for researchers and practitioners.