Green crystalline salts of substituted pyridinium oxopentachloromolybdates(V) were obtained from concentrated hydrochloric acid solution of molybdenum(V)-thiocyanate extract. $MoOCl_3(X-py)_2$ (X-py were 4-and 3-cyanopyridine, 2-amino-4-picoline and 4-acetylpyridine) were obtained by reflux of the corresponding substituted pyridinium salts of oxopentachloromolybdates(Ⅴ) in absolute ethanol. ($X-pyH_2$)[$MoOCl_5$]$H_2$O containing the $MoO^{3+}$ group are dissolved and hydrolysed in water but $MoOCl_3(X-py)_2$ are insoluble in water, alcohol and acetone. The complexes are paramagnetic compounds