A new bath formulation was developed, which allowed deposition of copper-rich Cu-Ni-P alloys in electroless acidic solutions in the absence of formaldehyde. The reducing agent was sodium hypophosphite. Though cupric ions do not catalyse the oxidation of hypophosphite, we show that, in the presence of a low concentration of Ni(II) species, it is possible, even at low pHs, to induce the reduction of the cupric species. A very strong preferential deposition of copper was observed, which gives Cu-Ni-P layers with copper content up to 97 wt%. The phosphorus content decreased from 13% to 1% with increasing copper content. The plating rate decreased when the copper sulfate concentration in the solution increased. It increased with increasing pH or temperature, but the influence was less pronounced than in alkaline solutions. Compact layers were obtained with a nodular morphology which did not markedly changed with composition.