I've found several valid invocations of _mm256_cmp_ps() that will make valgrind crash with a VEX error.

It turns out that the compare variant (in third parameter) is poorly supported by VEX.
For instance, using '_CMP_NEQ_OS' will cause a crash.
As does '__CMP_GE_OQ'.
However, using ' _CMP_GT_OQ' is fine.

There are many possible values for the compare variant:
/* Compare */
#define _CMP_EQ_OQ    0x00 /* Equal (ordered, non-signaling)  */
#define _CMP_LT_OS    0x01 /* Less-than (ordered, signaling)  */
#define _CMP_LE_OS    0x02 /* Less-than-or-equal (ordered, signaling)  */
#define _CMP_UNORD_Q  0x03 /* Unordered (non-signaling)  */
#define _CMP_NEQ_UQ   0x04 /* Not-equal (unordered, non-signaling)  */
#define _CMP_NLT_US   0x05 /* Not-less-than (unordered, signaling)  */
#define _CMP_NLE_US   0x06 /* Not-less-than-or-equal (unordered, signaling)  */
#define _CMP_ORD_Q    0x07 /* Ordered (nonsignaling)   */
#define _CMP_EQ_UQ    0x08 /* Equal (unordered, non-signaling)  */
#define _CMP_NGE_US   0x09 /* Not-greater-than-or-equal (unord, signaling)  */
#define _CMP_NGT_US   0x0a /* Not-greater-than (unordered, signaling)  */
#define _CMP_FALSE_OQ 0x0b /* False (ordered, non-signaling)  */
#define _CMP_NEQ_OQ   0x0c /* Not-equal (ordered, non-signaling)  */
#define _CMP_GE_OS    0x0d /* Greater-than-or-equal (ordered, signaling)  */
#define _CMP_GT_OS    0x0e /* Greater-than (ordered, signaling)  */
#define _CMP_TRUE_UQ  0x0f /* True (unordered, non-signaling)  */
#define _CMP_EQ_OS    0x10 /* Equal (ordered, signaling)  */
#define _CMP_LT_OQ    0x11 /* Less-than (ordered, non-signaling)  */
#define _CMP_LE_OQ    0x12 /* Less-than-or-equal (ordered, non-signaling)  */
#define _CMP_UNORD_S  0x13 /* Unordered (signaling)  */
#define _CMP_NEQ_US   0x14 /* Not-equal (unordered, signaling)  */
#define _CMP_NLT_UQ   0x15 /* Not-less-than (unordered, non-signaling)  */
#define _CMP_NLE_UQ   0x16 /* Not-less-than-or-equal (unord, non-signaling)  */
#define _CMP_ORD_S    0x17 /* Ordered (signaling)  */
#define _CMP_EQ_US    0x18 /* Equal (unordered, signaling)  */
#define _CMP_NGE_UQ   0x19 /* Not-greater-than-or-equal (unord, non-sign)  */
#define _CMP_NGT_UQ   0x1a /* Not-greater-than (unordered, non-signaling)  */
#define _CMP_FALSE_OS 0x1b /* False (ordered, signaling)  */
#define _CMP_NEQ_OS   0x1c /* Not-equal (ordered, signaling)  */
#define _CMP_GE_OQ    0x1d /* Greater-than-or-equal (ordered, non-signaling)  */
#define _CMP_GT_OQ    0x1e /* Greater-than (ordered, non-signaling)  */
#define _CMP_TRUE_US  0x1f /* True (unordered, signaling)  */

Valgrind VEX only supports some of them.

vex amd64->IR: unhandled instruction bytes: 0xC4 0x41 0x7C 0xC2 0xEF 0x1C 0xC4 0x41
vex amd64->IR:   REX=0 REX.W=0 REX.R=1 REX.X=0 REX.B=1
vex amd64->IR:   VEX=1 VEX.L=1 VEX.nVVVV=0x0 ESC=0F
vex amd64->IR:   PFX.66=0 PFX.F2=0 PFX.F3=0
==30317== valgrind: Unrecognised instruction at address 0x42b25b.