Hierarchically structured materials (HSMs) are becoming increasingly important in catalysis, separation and energy applications due to their advantageous diffusion and flux properties. Here, we introduce a facile modular approach to fabricate HSMs with tailored functional conducting polypyrrole microparticles (PPyMP). The PPyMPs were fabricated with a calcium carbonate (CaCO3) template-assisted polymerization technique in aqueous media at room temperature, thus providing a new green chemistry for producing water-processable functional polymers. The sacrificial CaCO3 template guided the polymerization process to yield homogenous PPyMPs with a narrow size distribution. The porous nature of the CaCO3 further allows the incorporation of various organic and inorganic dopants such as an electrocatalyst and redox mediator for the fabrication of functional PPyMPs. Dawson-type polyoxometalate (POM) and methylene blue (MB) were chosen as the model electrocatalyst and electron mediator dopant, respectively. Hierarchically structured electrochemical interfaces were created simply by self-assembly of the functional PPyMPs. We demonstrate the versatility of this technique by creating two different hierarchical structured electrochemical interfaces: POM-PPyMPs for hydrogen peroxide electrocatalysis and MB-PPyMPs for mediated bioelectrocatalysis. We envision that the presented design concept could be extended to different conducting polymers doped with other functional organic and inorganic dopants to develop advanced electrochemical interfaces and to create high surface area electrodes for energy storage.