Based on the effective Hamiltonian with the generalized factorization approach, we calculate the branching ratios and CP asymmetries of B → VV decays in the Topcolor-assisted Technicolor (TC2) model. Within the considered parameter space we find that: (a) for the penguin-dominated and decays, the new physics enhancements to the branching ratios are around 40%; (b) the measured branching ratios of and decays prefer the range of ; (c) the SM and TC2 model predictions for the branching ratio are only about half of the Belle's measurement; and (d) for most B → VV decays, the new physics corrections on their CP asymmetries are generally small or moderate in magnitude and insensitive to the variation of and .