The traditional optimization algorithm of communication resource allocation in a complex network has the disadvantage of weak antijamming ability, and the communication quality decreases obviously when the number of users is large. In China’s large urban network applications, mobile phones and other networks can have problems such as reduced network efficiency when there are more access users at some communication base stations, thus affecting user network usage. An optimization algorithm of communication resource allocation in the complex network based on an improved neural network is proposed. Increase inertia improves the traditional BP neural network algorithm, using the average path length, clustering coefficient, and connectivity distribution index analysis of the complex network; the improved Hopfield neural network is utilized to confirm each user volume size; it is concluded that their users are able to get the number of subchannels, through the instantaneous channel coarse pair gain dynamic channel allocation, calculating bit load matrix at the same time, minimize transmission power, and achieve bit loading and power allocation and communication resource allocation optimization. Experimental results show that the proposed method has better application performance by introducing the improved neural network and suppressing the external interference on the basis of enhancing the communication effect.