In this work, we first formulate the Tsallis entropy in the context of complex networks. We then propose a network construction whose topology maximizes the Tsallis entropy. The growing network model has two main ingredients: copy process and random attachment mechanism (C-R model). We show that the resulting degree distribution exactly agrees with the required degree distribution that maximizes the Tsallis entropy. We also provide another example of network model using a combination of preferential and random attachment mechanisms (P-R model) and compare it with the distribution of the Tsallis entropy. In this case, we show that by adequately identifying the exponent factor q, the degree distribution can also be written in the q-exponential form. Taken together, our findings suggest that both mechanisms, copy process and preferential attachment, play a key role for the realization of networks with maximum Tsallis entropy. Finally, we discuss the interpretation of q parameter of the Tsallis entropy in the context of complex networks. (C) 2009 Elsevier B.V. All rights reserved.