Passive small direct alcohol fuel cells (PS-DAFCs) are compact, standalone devices capable of electrochemically converting the chemical energy in the fuel/alcohol into electricity, with low pollutant emissions and high energy density. Thus, PS-DAFCs are extremely attractive as sustainable/green off-grid low-power sources (milliwatts to watts), considered as alternatives to batteries for small/portable electric and electronic devices. PS-DAFCs benefit from long life operation and low cost, assuring an efficient and stable supply of inherent non-polluting electricity. This review aims to assess innovations on PS-DAFC technology, as well as discuss the challenges and R&D needs covered on practical examples reported in the scientific literature, since 2018. Hence, this compilation intends to be a guidance tool to researchers, in order to help PS-DAFCs overcome the barriers to a broad market introduction and consequently become prime renewable energy converters and autonomous micropower generators. Only by translating research discoveries into the scale-up and commercialization process of the technology can the best balance between the economic and technical issues such as efficiency, reliability, and durability be achieved. In turn, this will certainly play a crucial role in determining how PS-DAFCs can meet pressing sustainable energy needs.