Niobium and tantalum are found together in natural minerals. Leaching with concentrated acid solution or alkaline roasting followed by water/dilute acid leaching results in a solution containing these two metals. In this work, we reviewed the extraction and separation of Nb(V) and Ta(V) from leach liquors in the absence and presence of hydrofluoric acid by acidic, neutral extractants and amines. Several solvent extraction systems were compared in the light of the requirement of hazardous chemicals, extraction/separation efficiency, and stability/solubility of extractants. Since the cationic species of Nb(V) and Ta(V) are unstable in the aqueous solution, the application of acidic extractants for extraction and separation of these metals is limited. Amines can extract Nb(V) as well as Ta(V) irrespective of the presence of fluoride ion but the separation of these metals from the loaded amines should be carried out in stripping process, resulting in process complexity. Another disadvantage encountered for amine is related to high viscosity in extraction process. Neutral extractants are considered as promising extractants which are effective to separate Ta(V) and Nb(V) from either non-fluoride or to moderate fluoride ion concentration in terms of extraction, separation and stripping efficiency. Compared to the traditional methyl iso-butyl ketone (MIBK) based system, methyl isoamyl ketone (MIAK) is found to be a promising extractant to separate Nb(V) and Ta(V).