Nowadays the main sources of energy are petroleum, coal, and natural gas. However, these fossil sources are not reproduced in nature; on a human timescale their reserves are exhausted permanently and run down. Considerable attention in recent years has been given to plant biomass, which in contrast to the fossil sources is continuously renewed in nature. In this critical review the use of non-edible plant biomass for production of various kinds of biofuels is considered. To generate energy, plant biomass either can be burned directly or it can be used after its conversion into carbonized solid fuel (e.g. biochar), liquid fuels (bioethanol, biodiesel, bio-oil), or gases (biogas). Among various biofuels, production of bioethanol has potential to be the most attractive if recent technological advances become implemented, such that the co-production of ethanol and valuable byproducts can be combined together with recycling of solid and liquid wastes. A comparative analysis of energetic potential of biomass and various kinds of biofuels revealed that the most efficient way to produce energy is by direct burning of the plant biomass in a pelletized form, while the burning of such amount of the solid, liquid, or gaseous biofuel, which can be obtained from the plant material, gives a much smaller energetic effect. Novel types of pellets, as well as solid/liquid biofuels, having improved fuel characteristics are described.