Approximately one-quarter of the total greenhouse gases (GHG) emissions in Europe can be attributed to the transport sector, with petroleum-derived fuels dominating road transport. In the current environmental and economic context, the use of less polluting alternative fuels simultaneously providing security of supply and optimal energy storage is encouraged. Natural gas (NG) technology for transportation is mature and extended through the use of the compressed form in urban and light vehicles. The introduction of liquefied natural gas (LNG) could broaden the use of natural gas for longer distances due to its higher energy density. In addition, the use of LNG in heavy-duty vehicles reduces the GHG emissions per kilometer by up to 20% and eliminates almost 100% of the sulfur oxides and particulate matter while also reducing the noise in inner cities compared with the use of diesel trucks. This paper reviews the key environmental, technical and socioeconomic aspects of LNG deployment as alternative fuel for road freight transport. Although it is necessary to continue research to develop a reliable database to estimate the actual environmental impact of LNG, the main difficulties for its deployment are market-related. From this market perspective, the prospects for LNG introduction in the European scenario have also been analyzed. Ensuring price stability and reducing uncertainty for investments are keys. Steps taken to date for developing an open and transparent international NG market are paving the way. In addition, the installation of new LNG terminals would significantly contribute to the security of supply and meeting diversification targets. Finally, some projections for the LNG implementation in the Spanish road freight transport are introduced, concluding that the fuel switch in long-haul trucks could reduce GHG emissions by 12% and diesel fuel consumption by 42% in the long term.