请问下8U DSolve是否可以直接把矩阵作为输入参数

可以, 问题可能在于Mathematica中不区分行矢量和列矢量, 而你在输入的时候把它们用不同的List结构区分了
比如求解矩阵形式的薛定谔方程, 描述了自旋在磁场中的进动

sol = NDSolveValue[{I psi'[t] == PauliMatrix[3] . psi[t],
psi[0] == {0.6, 0.8}}, psi, {t, 0, 30}];
Plot[Evaluate[Conjugate[sol@t] . PauliMatrix[1] . sol@t], {t, 0, 30}]

可以的, 比如最简单的形式

初态为相干态, 就有
ClearAll["Global`*"];
{Doa, \[Alpha], \[Kappa]} = {25, 3., 0.1};
create[dim_?IntegerQ] :=
SparseArray[Band[{2, 1}] -> Sqrt@Range[1, dim - 1], {dim, dim}];
coherent[\[Alpha]_?NumericQ, dim_?IntegerQ] :=
Exp[-Abs[\[Alpha]]^2/2]*
Table[\[Alpha]^n/Sqrt[n!], {n, 0, dim - 1, 1}];
adag = create[Doa];
a = Transpose@adag;
rho0 = Outer[Times, coherent[\[Alpha], Doa],
Conjugate@coherent[\[Alpha], Doa]];
\[Rho] =
NDSolveValue[{\[Rho]'[
t] == \[Kappa]*a . \[Rho][t] . adag - \[Kappa]/2*
adag . a . \[Rho][t] - \[Kappa]/2*\[Rho][t] . adag . a, \[Rho][
0] == rho0}, \[Rho], {t, 0, 20}]; Plot[{Re@
Tr[adag . a . \[Rho][t]], Abs[\[Alpha]]^2*Exp[-\[Kappa] t]}, {t, 0,
20}, PlotStyle -> {{RGBColor["#4FBDFF"]}, {Black, Dashed}},
PlotRange -> {{0, 20}, {0, 10}},
Ticks -> {Range[0, 20, 5], Range[0, 10, 2]},
AxesLabel -> {"time", "average photon number"},
PlotLegends -> {"numerical result", "analytic result"}]