A novel layered germanate compound, |(C6N4H21)2|[Ge7O14F6] (JU‐86, JU = Jilin University), was solvothermally synthesized. Its structure consists of 4.6‐net sheets built up from dissymmetric 83 building units. Different from those found in several metal phosphate compounds, half of the 4.6‐net sheets in JU‐86 are constructed from right‐handed 83 building units and the other half are constructed from left‐handed ones. Right‐handed and left‐handed 4.6‐net sheets are stacked alternately in JU‐86. Each 4.6‐net sheet is sandwiched by two layers of protonated tris(2‐aminoethyl)amine (tren) molecules to form an unusual pseudo triple‐sheet layer through hydrogen‐bonding interactions. No hydrogen bonds are found between different pseudo triple‐sheet layers.