We prepared polyoxomolybdates with methylammonium countercations from methylammonium monomolybdate, (CH3NH3)2[MoO4], through two dehydrative condensation methods, acidifying in the aqueous solution and solid-state heating. Discrete (CH3NH3)10[Mo36O112(OH)2(H2O)14], polymeric ((CH3NH3)8[Mo36O112(H2O)14])n, and polymeric ((CH3NH3)4[γ-Mo8O26])n were selectively isolated via pH control of the aqueous (CH3NH3)2[MoO4] solution. The H2SO4-acidified solution of pH < 1 produced "sulfonated α-MoO3", polymeric ((CH3NH3)2[(MoO3)3(SO4)])n. The solid-state heating of (CH3NH3)2[MoO4] in air released methylamine and water to produce several methylammonium polyoxomolybdates in the sequence of discrete (CH3NH3)8[Mo7O24-MoO4], discrete (CH3NH3)6[Mo7O24], discrete (CH3NH3)8[Mo10O34], and polymeric ((CH3NH3)4[γ-Mo8O26])n, before their transformation into molybdenum oxides such as hexagonal-MoO3 and α-MoO3. Notably, some of their polyoxomolybdate structures were different from polyoxomolybdates produced from ammonium molybdates, such as (NH4)2[MoO4] or (NH4)6[Mo7O24], indicating that countercation affected the polyoxomolybdate structure. Moreover, among the tested polyoxomolybdates, (CH3NH3)6[Mo7O24] was the best negative staining reagent for the observation of the SARS-CoV-2 virus using transmission electron microscopy.