Light alkanes are the most abundantly available carbon-based feedstocks on earth and as major constituents of natural gas and oil-associated gas. Compared with oil, natural gas is considered a greener fuel and promising alternative for energy and chemical production. However, the grand challenge in the chemistry of light alkanes utilization is the development of an efficient method for the selective activation C–H bond. The transportation issue comes from the low boiling point. On the other hand, these unactivated molecules are hard to be activated under mild conditions because of their high bond dissociation energy and low acidity. Moreover, the functionalized products, such as ethylene or methanol, have higher reactivity than light alkanes. Due to these challenges, it is vital that develop efficient processes to achieve value-added convert under economic and green reaction conditions. In this review, we summarized the recent progress in the field of homogeneous functionalizations of light alkanes and was subtitled to four different aspects according to the mechanism, including electrophilic substitution, oxidative addition, carbene insertion, and free radical substitution. However, developing a new, lower temperature, economic, and green direct light alkanes conversion process is still needed to address.