Selective cascade conversion of cellulose into valuable C2 or C4 products over acid catalysts is still not fully explored because glucose-fructose isomerization followed by fructose conversions is thermodynamically easy to occur during the reaction, leading the formation of C6, C5, C3 and C1 products such as 5-hydroxymethylfurfural (HMF), levulinates, lactates, formates, and so on. In this study, phosphomolybdates (PMo) with the Keggin structure was found to promote cascade oxidation of cellulose conversion via selective aldohexoses pathways, i.e. an epimerization and a [2+ 4] retro-aldol of glucose/mannose, rather than aldo-ketohexoses routes, i.e. a glucose-fructose isomerization and a [3+3] retro-aldol of fructose, which produced glycolic acid (GlycA) (C2) as the main product (similar to 50% selectivity). Either in aerobic or anaerobic state, PMo selectively catalyzed glucose epimerization into mannose at < 100 degrees C (similar to 95% selectivity) and effectively promoted the [2+ 4] retro-aldol reaction of these aldohexoses at > 100 degrees C. This behavior is completely different from that of molybdate in MoO3 which is only effective for the epimerization reaction (the Bilik reaction). In this cascade oxidation reaction, PMo was reduced into heteropoly-blue (PMored) as observed by the color change of the solution, UV-VIS and FT-IR measurements. In this case, the molecular oxygen was found to reoxidize PMored into PMo, leading the catalytic activity to be remained stable. The results shown in this study provide an insight for the catalyst development on selective synthesis of C2, C4 and/or other novel valuable chemicals from carbohydrates via the aldohexose pathways.