Under photon excitation, 2D materials experience cascading energy transfer from electrons to optical phonons (OPs) and acoustic phonons (APs). Despite few modeling works, it remains a long‐history open problem to distinguish the OP and AP temperatures, not to mention characterizing their energy coupling factor (
G
). Here, the temperatures of longitudinal/transverse optical (LO/TO) phonons, flexural optical (ZO) phonons, and APs are distinguished by constructing steady and nanosecond (ns) interphonon branch energy transport states and simultaneously probing them using nanosecond energy transport state‐resolved Raman spectroscopy. Δ
T
OP −AP
is measured to take more than 30% of the Raman‐probed temperature rise. A breakthrough is made on measuring the intrinsic in‐plane thermal conductivity of suspended nm MoS
2
and MoSe
2
by completely excluding the interphonon cascading energy transfer effect, rewriting the Raman‐based thermal conductivity measurement of 2D materials.
G
OP↔AP
for MoS
2
, MoSe
2
, and graphene paper (GP) are characterized. For MoS
2
and MoSe
2
,
G
OP↔AP
is in the order of 10
15
and 10
14
W m
−3
K
−1
and
G
ZO↔AP
is much smaller than
G
LO/TO↔AP
. Under ns laser excitation,
G
OP↔AP
is significantly increased, probably due to the reduced phonon scattering time by the significantly increased hot carrier population. For GP,
G
LO/TO↔AP
is 0.549 × 10
16
W m
−3
K
−1
, agreeing well with the value of 0.41 × 10
16
W m
−3
K
−1
by first‐principles modeling.