We investigated complex magnetic properties of multifunctional LaCrO3-LaFeO3 system. The magnetic measurements substantiate the presence of competing complex magnetic ordering against temperature, showing paramagnetic to ferrimagnetic transition at ∼300 K, followed by antiferromagnetic (AFM) transition near ∼250 K superimposed on ferrimagnetic phase. The onset of weak ferrimagnetic ordering is attributed to the competing complex interaction between two AFM LaCrO3-LaFeO3 sublattices. The low-Temperature AFM ordering is also substantiated by temperature-dependent Raman measurements, where the intensity ratio of 700 cm-1 Raman active mode showed a clear enhancement with lowering the temperature. The non-saturating nature of magnetic moments in LaCrO3-LaFeO6 suggests the predominating AFM ordering in conjunction with ferrimagnetic ordering between 250 K-300 K up to 5 T magnetic field. A complex magnetic structure of LaCrO3-LaFeO3 is constructed, emphasizing the metastable magnetic phase near room temperature and low-Temperature antiferromagnetic state. © 2020 IOP Publishing Ltd.