Abstract The determination of inorganic arsenic species in food has become very important during the last few years, since As(III) and As(V) are considered carcinogenic and found at high concentrations in food products, such as rice. The present work describes the development of three different methods for the determination of total arsenic, total inorganic arsenic, and As(III)–As(V) in rice and rice flour food products, purchased from the local market by electrothermal atomic absorption spectrometry (ETAAS). The methods were based on the use of different selective extraction procedures and the optimization of all crucial instrumental and methodological parameters. By these new preparation procedures for the determination of arsenic species, the loss and transformation of analytes during the extraction and digestion steps was prevented. For the validation of each method, precision, accuracy, and selectivity have been assessed, as performance criteria. All developed methods were accurate and precise. The calculated recoveries ranged between 92% and 105% and the (%) relative standard deviation values, under repeatability or reproducibility conditions, were lower than 15% for all different concentration levels tested. The validated methods were applied successfully for the determination of total arsenic and total inorganic arsenic in a proficiency test organized by the International Measurement Evaluation Program (IMEP-107). The methods were also applied in rice and rice flour samples purchased from the Greek market and the obtained results indicated that in almost all samples total arsenic and total inorganic arsenic were detected at ng/g levels.