So, I believe you work in the category of $R$-modules for some commutative ring, or any abelian category with a monoidal structure and an internal hom. Otherwise, there are a priori no internal hom in the category of chain complexes.
If $C^*=D^*$ is as you described, the internal hom you wrote is not correct. It is rather :
$$\operatorname{hom}^*(C^*,C^*)=\operatorname{hom}(C^0,C^0)\times \operatorname{hom}(C^1,C^1)\rightarrow \operatorname{hom}(C^0,C^1)$$
with differential being $(f,g)\mapsto df-gd$.
Then, $\operatorname{hom}^*(C^*,C^*)\otimes C^*$ is the complex
$$\begin{align}\operatorname{hom}(C^0,C^0)\times \operatorname{hom}(C^1,C^1)\otimes C^0\rightarrow\\ \operatorname{hom}(C^0,C^1)\otimes C^0\oplus (\operatorname{hom}(C^0,C^0)\times \operatorname{hom}(C^1,C^1))\otimes C^1\rightarrow& \operatorname{hom}(C^0,C^1)\otimes C^1\end{align}$$
The first differential is given by $(f,g)\otimes c\mapsto (df-gd)\otimes c \oplus (f,g)\otimes dc$. The second differential is given by $u\otimes c_0\oplus (f,g)\otimes c_1\mapsto (df-gd)\otimes c_1$.
The evaluation map is the map to the complex $C^0\rightarrow C^1$ given
- in degree 0 by : $(f,g)\otimes c\mapsto f(c)$
- in degree 1 by : $u\otimes c_0 \oplus (f,g)\otimes c_1\mapsto u(c_0)+g(c_1)$
Let us check that this is indeed a morphism of complexes, in other words, let us check that these maps commute with the differentials. There are only one commutative square to check :
The first is
$$\require{AMScd}
\begin{CD}
\operatorname{hom}(C^0,C^0)\times \operatorname{hom}(C^1,C^1)\otimes C^0@>>>\operatorname{hom}(C^0,C^1)\otimes C^0\oplus (\operatorname{hom}(C^0,C^0)\times \operatorname{hom}(C^1,C^1))\otimes C^1\\
@VVV@VVV\\
C^0@>>>C^1
\end{CD}
$$
the map going through the left arrow is $(f,g)\otimes c\mapsto f(c)\mapsto d(f(c))$. While the map going through the above arrow is $$(f,g)\otimes c\mapsto (df-gd)\otimes c\oplus (f,g)\otimes dc\mapsto d(f(c))-g(dc) + g(dc)=d(f(c))$$
So the square is indeed commutative.