It is a significant challenge to develop a high-efficiency synthetic methodology to access fully conjugated 2D conjugated polymer (CP)/covalent organic framework (COF) nanosheets (NSs) that have great application potential for electronics and energy. Herein, we report the exfoliation of a series of amorphous ethynyl-linked phthalocyanine (Pc) CPs (MPc-CPs, M = Fe, Co, Fe0.5Co0.5) into ultrathin MPc-CP NSs. Random coupling between the four regioisomers (with D4h, D2h, C2v and Cs symmetry) of the two tetra-β-substituted phthalocyanine precursors endows the resulting phthalocyanine conjugated polymers MPc-CPs with intrinsic structural defects and a disordered framework on individual layers. This in turn induces a diminished interlayer overlapping and a weakened interlayer π–π stacking interaction, facilitating the possible exfoliation of MPc-CPs into ultrathin 2D NSs with a yield of over 50%. The direction observation by transmission electron microscopy (TEM) and atomic force microscopy (AFM) demonstrates that the ultrathin MPc-CP NSs possess a smooth surface with a uniform thickness of 1–3 nm and a lateral size of hundreds of nanometers. The as-prepared bimetallic Fe0.5Co0.5Pc-CP NSs were further used to fabricate a heterostructure Fe0.5Co0.5Pc-CP NS@G with graphene NSs as an oxygen reduction reaction (ORR) catalyst, which exhibits an onset potential of 1006 mV and a half-wave potential of 927 mV in 0.1 M KOH, representing one of the best values in an alkaline medium. Moreover, the excellent ORR activity of the exfoliated tetrapyrrole-based conjugated NSs hybridized with graphene has also been demonstrated by a Zn–air battery device, showing an open circuit voltage of 1.34 V and a peak power density of ca. 180 mW cm−2.