The structure of biomass direct fired boiler differs greatly from that of common fuel powder boiler, so the difference of operation process is great, which will inevitably lead to the difference of operation regulation law. Therefore, it is very important to analyze its technological process and combustion process in detail. All data were analyzed by SPSS17.0. We used the IBM SPSS Modeler 14.1data software to carry out modeling and prediction. The results show that there are 100 neurons in hidden layer and the area under the curve. The model accuracy, sensitivity and specific is 91.96%, 81.22% and 93.77%. Through validation data set validating, the model accuracy, sensitivity and specific is 92.15%, 80.32% and 94.01%. Therefore working process of biomass combustion boiler could accurately predict by MLP neural network model based on characteristics as the input layer variables of prediction model.