Variational Monte Carlo (VMC) and fixed-node diffusion Monte Carlo (DMC) calculations are performed for S-4. The effect of single- and multireference trial functions, as well as choice of orbitals, is investigated for its effect on the quality of the Monte Carlo estimates. Estimates of symmetric (two S-2 molecules) and asymmetric (S atom and S-3 molecule) bond dissociation are reported. The conformational change Of S4 from C-2v to D-2h defines a double-well potential and is also estimated. Multireference DMC with natural orbitals (DMC/NO) estimates the energy of the conformational change as 1.20(20) kcal/mol; the dissociation of the long S-S single bond is estimated at 21.1(1.3) kcal/mol, and the asymmetric bond energy is estimated as 53.2(2.4) kcal/mol. An estimate of the total atomization energy using multireference DMC/NO gives a value of 219.5(2.2) kcal/mol. The relative quality of result and implications for simplified trial function design are discussed.