Olivine structure LiMnPO4 has been considered as one of the very promising electrodes for lithium-ion batteries because of their low cost, low toxicity and high voltage plateau compared with LiFePO4. In order to improve the electrochemical performance a key challenge in the field of lithium-ion battery, is to explore and invent suitable synthetic route to control the size and morphology of LiMnPO4. Here a detailed study exploring the novel route of microwave-hydrothermal (MH) synthesis for successfully obtaining LiMnPO4 crystals within few minutes is reported and the reaction process discussed in detail. Variation of the synthetic parameters show that a decrease in reactant concentration could lead to LiMnPO4 nano-platelets orientated in the ac plane with a very high electrochemical performance. The effect of the starting precursor (like, Mn) concentration as a means to tailor LiMnPO4 electrochemical performance is discussed. The effect of alteration of size, morphology, lattice parameters and crystal structure induced by addition of additives like citric acid (H3cit) and sodium dodecyl benzene sulfonate (SDBS) is further described and an example of the first reversible discharge of a product treated with H3cit obtained by MH route as high as 89.0mAh/g, is shown. The general investigation demonstrates that there is a relationship among microwave irradiation condition, crystal structure, morphology and electrochemical performance that can be exploited for the design of next generation lithium batteries.