Microwave‐assisted sample preparation was a major developmental step in combining the overall quality and speediness of spectrochemical analysis with the initial step of converting solid samples into representative solutions. Instrumentation and applications for organic and inorganic samples are discussed in detail after briefly addressing the fundamentals of the method. The feasibility of using diluted acid solutions and pressurized oxygen vessels for sample digestion is rationalized and clearly related to recent advances in reaction vessel materials and the interaction between matter and microwave radiation. Applications based on microwave‐induced combustion (MIC) and procedures developed for chemical speciation are also highlighted. A list of ideal attributes for microwave‐assisted sample preparation is proposed and evaluated considering the state of the art. Major needs, mainly related to the capacity of digesting large sample masses and improvements in sample throughput, are also pointed out.