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The electron-doped Ca0.85La0.15MnO3 system exhibits a charge ordering transition at ∼135 K (TCO) with the antiferromagnetic Néel temperature at 160 K (TN). The resistivity data above and below TN (down to 90 K) are found to follow the small polaron hopping conduction mechanism. The corresponding activation energy, estimated from the theoretical fitting of resistivity data, shows an anomalous increase below TN, supporting the aforementioned charge ordering phenomenon. This result is further confirmed from fitting of the current–voltage (I–V) data with the small polaron hopping model. As revealed from the field cooled and zero field cooled magnetization measurements, this electron-doped system exhibits the signature of magnetic frustration, below TCO associated with phase separation behavior.