Carbon nanostructures have attracted great attention in recent years as novel electrode materials in batteries with increased capacity and conductivity as well as enhanced material stability. In these nanostructures, nanocarbons such as carbon nanotubes and graphene nanoplatelets are interconnected to construct their three-dimensional networks around the host materials for Li deposition. This work focuses on the study of electron transport phenomena in these nanocarbon networks with two model material systems: (1) single-walled carbon nanotube (SWCNT) networks co-embedded with silica microparticles (Fig. (a)), and (2) free-standing three-dimensional graphene (3DG) structures with polymeric surface modifications (Fig. (b)). We characterize the materials for electrical conductivity and thermopower with varying material contents in the composites to reveal several key factors determining their energy-dependent carrier transport characteristics. It is found that in these three-dimensional nanocarbon networks, carrier tunneling at the junctions between nanocarbons along with the network morphology predominantly determines the transport properties. Simultaneous increase in electrical conductivity and thermopower is achieved for SWCNT networks co-embedded with silica microparticles by increasing silica content up to 40 w.t.% at a fixed CNT content. The enhanced electron transport is attributed to the reduced junction distances due to the intimate network formation on the surface of silica particles with a polymer binder. Our transport theory based on the Landauer formalism for junction tunneling reveals that the junction modification with polymer can alter the potential barrier heights for both electrons and holes at the junction to significantly change the transport properties of the composite. Doping of nanocarbons is also investigated for their impacts on the junction transport and the geometric factor of the networks. Finally, we also investigate the use of these carbon nanostructures in solid-state thermoelectric (TE) energy harvesters and ionic TE capacitors to harvest thermal energy from temperature gradients and fluctuations. Figure 1