This study was set out to chiefly examine the influence of psychological traits—need of achievement (“N of Ach”) and risk-taking propensity (RTP)—on perceived usefulness (PUF) and perceived ease of use (PercEU), as well as their effects on the intention to use e-commerce among rural micro-entrepreneurs. This study exploited the psychological traits theories and the technology acceptance model (TAM) by utilizing samples represented by rural micro-entrepreneurs. The results of the study found that the N of Ach and RTP significantly influence PUF and PercEU. The two original TAM constructs and PercEU have significant relationships with PUF and intention. At the same time, it was also found that there exists a significant relationship between PUF and intention. This study therefore serves to fill the gaps where N of Ach and RTP of rural micro-entrepreneurs are seldom tested to examine the effects of perceptions of benefits and ease of use on the adoption of e-commerce. On top of that, this study provides vital input to policy makers and stakeholders of rural development in their efforts to increase the adoption of e-commerce among rural micro-entrepreneurs.