Asymmetric alkyl carbonate solvents (ACS) have been used as components of liquid electrolyte systems designed for Li-ion cells. Four ACS were selected: methyl-propyl carbonate (MPC), ethyl-propyl carbonate (EPC), methyl-isopropyl carbonate (MiPC) and ethyl-isopropyl carbonate (EiPC). The common features of all these ACS are a low melting point and a low viscosity, enhancing electrolytes conductivity toward low temperatures. The viscosity and the conductivity (salt: LiPF6, 1M) of the ACS and their mixtures with ethylene carbonate (EC, 50% v/v), were studied as a function of the temperature (T). Arrhenius types plots of the logarithm of the conductivity versus 1/T reveals that ACS and ACS/EC mixtures are vitreous at low temperatures. The electrochemical and cycling behaviors of a graphite anode and a LiCoO2 cathode have been evaluated using coin cells with a Li counter electrode. The charge and discharge capacities have been determined as a function of the cycle number. MiPC which builds an highly stable surface film on the graphite electrode, can be used as a single-solvent electrolyte with only a slight decrease in capacity of the LiCoO2 cathode. All ACS/EC mixtures exhibit good filming properties at the negative electrode and no capacity loose at the positive electrode. The ability of some of the electrodes–electrolyte systems to undergo increased rates of discharge (C/5 to C/2) has been also evaluated.