The invention discloses a pipeline leakage emergency instruction self-decision making system based on a monitoring network. The pipeline leakage emergency instruction self-decision making system based on the monitoring network comprises a monitoring terminal, a collector and a server, wherein the monitoring terminal comprises a leakage monitor, a flow velocity monitor, a flow rate monitor, an air condition monitor and an oil film thickness monitor; the collector is used for connecting with each of the monitors of the monitoring terminal, collecting an oil liquid leakage parameter, an environmental parameter and an oil film thickness parameter; the server is used for importing the oil liquid leakage parameter, the environmental parameter and the oil film thickness parameter into an improved Fay model, an improved Navy model, a Fingas evaporation equation and a Lagergren secondary adsorption speed equation for calculation, so that the diffusion parameter of the oil film is obtained.