To achieve insulating materials with a low-dielectric characteristic for high-frequency communication applications, three phosphinated poly(aryl ether)s: P1-act (with acetic moiety), P1-mma (with phenyl methacrylic moiety), and P1-vbe (with vinylbenzyl ether moiety) were modified from a phenol-functionalized phosphinated poly(aryl ether) (P1). P1-act and P1-mma, both with active ester linkages (Ph–O–(C=O)−), were reacted with three commercial epoxy resins (diglycidyl ether of bisphenol A, HP7200, and cresol novolac epoxy) to obtain secondary hydroxyl-free epoxy thermosets. Because of the secondary hydroxyl-free structure, epoxy thermosets cured by P1-act and P1-mma show an 11–15% reduction in dielectric constant than those cured by P1. P1-vbe, with reactive vinylbenzyl ether moieties, was self-cured to a high-performance thermoset with a T g value as high as 302 °C and a dielectric constant as low as 2.64 U . High- T g and low-dielectric thermosets have been developed in this work.