Crystalline symmetry is a defining factor of the electronic band topology in solids, where many-body interactions often induce a spontaneous breaking of symmetry. Superconductors lacking an inversion center are among the best systems to study such effects or even to achieve topological superconductivity. Here, we demonstrate that
T
RuSi materials (with
T
a transition metal) belong to this class. Their bulk normal states behave as three-dimensional Kramers nodal-line semimetals, characterized by large antisymmetric spin-orbit couplings and by hourglass-like dispersions. Our muon-spin spectroscopy measurements show that certain
T
RuSi compounds spontaneously break the time-reversal symmetry at the superconducting transition, while unexpectedly showing a fully gapped superconductivity. Their unconventional behavior is consistent with a unitary (
s
+
ip
) pairing, reflecting a mixture of spin singlets and spin triplets. By combining an intrinsic time-reversal symmetry-breaking superconductivity with nontrivial electronic bands,
T
RuSi compounds provide an ideal platform for investigating the rich interplay between unconventional superconductivity and the exotic properties of Kramers nodal-line/hourglass fermions.