The doubly charmed baryon decay Xi(++)(cc) -> Xi(+)(c)pi(+) is observed for the first time, with a statistical significance of 5.9 sigma, confirming a recent observation of the baryon in the Lambda K-+(c)-pi(+)pi(+) final state. The data sample used corresponds to an integrated luminosity of 1.7 fb(-1), collected by the LHCb experiment in pp collisions at a center-of-mass energy of 13 TeV. The Xi(++)(cc) mass is measured to be 3620.6 +/- 1.5(stat) +/- 0.4(syst) +/- 0.3(Xi(+)(c)) MeV/c(2) and is consistent with the previous result. The ratio of branching fractions between the decay modes is measured to be [B(Xi(++)(cc) -> Xi(+)(c)pi(+)) x B(Xi(+)(c) -> pK(-)pi(+))]/[B(Xi(++)(cc) -> Lambda K-+(c)-pi(+)pi(+)) x B(Lambda(+)(c) -> pK(-)pi(+))] = 0.035 +/- 0.009 (stat) +/- 0.003 (syst).