The invention provides a process for forming a multi-layer film including the steps of: (1) forming an under layer film onto a substrate by coating an under layer film material containing a resin represented by the following general formula (1) in which a compound having a bisnaphthol group has been made a novolac resin, and curing the same by heat treatment at a temperature in a range of 300° C. or higher and 700° C. or lower for 10 seconds to 600 seconds, (2) forming a silicon film onto the under layer film, (3) forming a hydrocarbon film onto the silicon film by coating a hydrocarbon film material, and (4) forming a silicon-oxidized film onto the hydrocarbon film by coating a silicon-oxidized film material. There can be provided a process for forming a multi-layer film which can reduce reflectance, and useful for a patterning process with high dimensional accuracy of dry etching.