Photodissociation dynamics of the OH bond of phenol is studied with an optimally shaped laser pulse. The theoretical model consists of three electronic states (the ground electronic state, ππ* state, and πσ* state) in two nuclear coordinates (the OH stretching coordinate as a reaction coordinate, r, and the CCOH dihedral angle as a coupling coordinate, θ). The optimal UV laser pulse is designed using the genetic algorithm, which optimizes the total dissociative flux of the wave packet. The latter is calculated in the adiabatic asymptotes of the S0 and S1 electronic states of phenol. The initial state corresponds to the vibrational levels of the electronic ground state and is defined as |nr, nθ⟩, where nr and nθ represent the number of nodes along r and θ, respectively. The optimal UV field excites the system to the optically dark πσ* state predominantly over the optically bright ππ* state with the intensity borrowing effect for the |0, 0⟩ and |0, 1⟩ initial states. For the |0, 0⟩ initial condition, the photodissociation to the S1 asymptotic channel is favored slightly over the S0 asymptotic channel. Addition of one quantum of energy along the coupling coordinate increases the dissociation probability in the S1 channel. This is because the wave packet spreads along the coupling coordinate on the πσ* state and follows the adiabatic path. Hence, the S1 asymptotic channel gets more (∼11%) dissociative flux as compared to the S0 asymptotic channel for the |0, 1⟩ initial condition. The |1, 0⟩ and |1, 1⟩ states are initially excited to both the ππ* and πσ* states in the presence of the optimal UV pulse. For these initial conditions, the S1 channel gets more dissociative flux as compared to the S0 channel. This is because the high energy components of the wave packet readily reach the S1 channel. The central frequency of the optimal UV pulse for the |0, 0⟩ and |0, 1⟩ initial states has a higher value as compared to the |1, 0⟩ and |1, 1⟩ initial states. This is explained with the help of an excitation mechanism of a given initial state in relation to its energy.