Comprehensive calculations of the Rh decoration effect on zigzag CNTs with n ranging from 7 to 12 were conducted in this work to understand the effect of Rh doping on geometric structures and electronic behaviors upon metallic and semiconducting CNTs. The obtained results indicated that Rh dopant not only contributes to the deformation of C-C bonds on the sidewall of CNTs, but also transforms the electron distribution of related complexes, thereby leading to a remarkable increase of the conductivity of pure CNTs given the emerged novel state within the energy gap for metallic CNTs and the narrowed energy gap for semiconducting CNTs. Our calculations will be meaningful for exploiting novel CNT-based materials with better sensitivity to electrons and higher electrical conductivity compared with pure CNTs.