Mechanical and rheological properties of novel dual-curing system based on sequential thiol-acrylate and thiol-epoxy reactions are studied with the aim of addressing the obtained materials to suitable advanced applications. The crosslinking process is studied by rheological analysis in order to determine conversion at gelation and the critical ratio. These parameters are used to discuss the intermediate material structure for each acrylate proportion and their possible application in the context of dual-curing and multi-step processing scenarios. Results from dynamo-mechanical analysis and mechanical testing demonstrate the high versatility materials under investigation and revealed a wide range of achievable final properties by simply varying the proportion between acrylate and thiol group. The intermediate stability between curing stages has been analysed in terms of their thermal and mechanical properties, showing that these materials can be stored at different temperatures for a relevant amount of time without experiencing significant effects on the processability. Experimental tests were made to visually demonstrate the versatility of these materials. Qualitative tests on the obtained materials confirm the possibility of obtaining complex shaped samples and highlight interesting shape-memory and adhesive properties.