a b s t r a c t Tris(hydroxymethyl)phosphine, P(CH 2 OH) 3 , a water-soluble compound, has been known for about 50 years but development of its coordination chemistry has been slow and relatively recent. During some collaborative studies with a pulp and paper research institute on testing water-soluble catalysts for hydrogenation of lignin in pulp and the unsaturated functionalities in lignin model compounds, with the aim of bleaching pulps, we discovered new, in situ, Ru-P(CH 2 OH) 3 hydrogenation catalysts. Interest in the coordination chemistry of this phosphine thus ensued, and this review covers this topic as well as the coordination chemistry of a diphosphine analogue, bis[bis(hydroxymethyl)phosphino]ethane, (HOCH 2 ) 2 P(CH 2 ) 2 P(CH 2 OH) 2 . The applications of the water-soluble metal complexes of these two phosphines in the areas of catalysis and medicinal drugs are also described. These phosphines, in the absence of metals, were found serendipitously to be effective bleaching agents for pulps (and also brightness stabilizing agents), and some relevant organo-phosphorus chemistry from our group is also briefly presented, particularly because of its possible significance in hydroformylation and hydrogenation processes catalyzed by metal-phosphine complexes.