The redox-active tetrathiafulvalene (TTF) is a good electron donor, and porphyrin is highly delocalized in cyclic pi-conjugated systems. The direct combination of the two interesting building units into the same molecule provides an intriguing molecular system for designing nonlinear optical (NLO) molecular materials. In the present paper, the second-order NLO properties of a series of monoTTF-porphyrins and metalloporphyrins have been calculated by density functional theory (DFT) combined with the finite field (FF) method. Our calculations show that these compounds possess considerably large static first hyperpolarizabilities, similar to 400 x 10(-30) esu. Since the TTF unit is able to exist in three different stable redox states (TTF, TTF center dot+, and TTF2+), the redox switching of the NLO response of the zinc(II) derivative of mono TTF-metalloporphyrin has been studied, and a substantial enhancement in static first hyperpolarizability has been obtained in its oxidized species according to our DFT-FF calculations. The beta values of one- and two-electron-oxidized species are 3.6 and 8.7 times as large as that of the neutral compound, especially for two-electron-oxidized species, with a value of 3384 x 10(-30) esu. This value is about 3 times that for a push-pull metalloporphyrin, which has an exceptionally large hyperpolarizability among reported organic NLO chromophores. Meanwhile, to give a more intuitive description of band assignments of the electron spectrum and trends in NLO behavior of these compounds, the time-dependent (TD)DFT method has been adopted to calculate the electron spectrum. The TDDFT calculations well-reproduce the soret band and Q-type bands of the mono TTF-porphyrin, and these absorption bands can be assigned to the pi -> pi* transition of the porphyrin core. On the other hand, the oxidized process significantly affects the geometrical structures of the TTF unit and porphyrin ring, and the two-electron-oxidized species has a planar TTF unit and a high conjugative porphyrin ring. This effect reduces the excited energy, changes the CT feature, and thus enhances its static first hyperpolarizability.